Fatty acid esters composition of a polyglycerine, and process for the preparation thereof

ABSTRACT

Disclosed are a fatty acid esters composition of a polyglycerine containing more than 70% of a fatty acid monoester which is defined by a specified analysis method, a process for the preparation thereof, a process for the preparation of a highly-purified fatty acid esters composition of a polyglycerine, and a highly-purified fatty acid esters composition of a polyglycerine having an oxirane oxygen concentration of below 100 ppm which is defined by a specified analysis method. 
     The fatty acid esters compositions of a polyglycerine are useful as additives for a variety of food-stuffs, additives for a variety of thermoplastic resins, and as additives for a variety of cosmetics or detergents.

This application is a divisional of Ser. No. 08/618,504 filed Mar. 19,1996 U.S. Pat. No. 6,278,008.

FIELD OF THE INVENTION

The present invention relates to a fatty acid esters composition of apolyglycerine containing more than 70% of a fatty acid monoester and aprocess for the preparation thereof.

Furthermore, the present invention relates to a highly-purified fattyacid esters composition of a polyglycerine and a process for thepreparation thereof.

Still further, the present invention relates to the use of the fattyacid esters compositions of a polyglycerine for an additive forfood-stuffs.

In addition, the present invention relates to a resin compositioncontaining the fatty acid esters compositions of a polyglycerine.

Besides, the present invention relates to compositions for cosmetics ordetergents containing the fatty acid esters compositions of apolyglycerine.

In more detail, the present invention relates to a fatty acid esterscomposition of a polyglycerine having an excellent emulsifying ability.The fatty acid esters compositions of a polyglycerine are useful as anadditive for food-stuffs, an additive for thermoplastic resins, and anadditive for cosmetics or detergents, etc.

BACKGROUND OF THE INVENTION

In recent, fatty acid esters of a polyglycerine are permitted as anadditive such as an emulsifier for food-stuffs, and demands in a marketare getting increased. The fatty acid esters composition of apolyglycerine have been usually employed in a variety of fields,particularly such as foods, as an emulsifier or an agent for adjusting aviscosity because esters having a wide range of HLB values can beobtained by the combination of polyglycerines having various molecularweight with fatty acids having various chain length which are startingmaterials, and it exhibits a higher stability in an acidic range.

As processes for preparing the fatty acid esters composition of apolyglycerine, there are exemplified; (1) an esterification reaction ofa polyglycerine with a fatty acid, (2) a transesterification reaction ofa polyglycerine with a fatty acid ester, (3) a transesterificationreaction of a polyglycerine with an oil and fatty acid, (4) an additionpolymerization reaction of glycidol to a monoglyceride of a fatty acid,and (5) an addition polymerization reaction of glycidol to a fatty acid,etc. Of the above-described reactions, the processes (2) and (3) areproblematic in the reactivity and the processes have many limitations inquality and purity of the fatty acid ester of a polyglycerine.

The process (1) is described in JAOCS (Journal of American Oil Chemists'Society), Vol. 58, page 878 (1981), in which there is carried out theesterification reaction of a polyglycerine with a fatty acid in thepresence of alkali catalysts to obtain a fatty acid ester of thepolyglycerine.

Furthermore, Japanese Patent Unexamined Publication (Kokai) No.41007/1994 discloses similar processes.

The process (5) is described in Japanese Patent Unexamined Publication(Kokai) No. 65705/1976, in which there is prepared a fatty acidmonoester of glycerine. However, the Publication states that there isobtained a carboxylic acid-1-monoglyceride having the polymerizationdegree of glycerine of 1 with a high percentage in the presence of aninert solvent, that is, it corresponds to a compound having n of average1 in the above-described chemical formula [1]. Notwithstanding, there isnot mentioned a fatty acid esters composition of a polyglycerine at allin the Publication.

As processes in which the addition polymerization reaction of glycidolis employed, there are exemplified the addition polymerization reaction[Japanese latent Examined Publication (Kokoku) No. 55254/1989, JapanesePatent Examined Publication (Kokoku) No. 11532/1992, Japanese PatentExamined Publication (Kokoku) No. 1291/1993] of glycidol to glycerine toobtain a polyglycerine employed in the processes (1) to (3), thepreparation of a polyglycerine [Japanese Patent Examined Publication(Kokoku) No. 69621/1992] by a hydrolysis reaction after the additionpolymerization reaction of glycidol to a fatty acid, and the preparationof polyglycerine monoalkylether or the preparation of polyglycerinemonoalkylthioether [U.S. Pat. Nos. 3,821,372, 3,966,398, and 4,087,466],etc.

However, in the preparation process of a polyglycerine by a hydrolysisreaction after the add polymerization reaction of glycidol to a fattyacid described in Japanese Patent Examined Publication (Kokoku) No.69621/1992, low fatty acids (a carbon number of 2 to 6) are employed asfatty acids to prepare polyglycerines, and a fatty acid ester of apolyglycerine is not mentioned at all.

Heretofore, a fatty acid monoester of a polyglycerine has been preparedby the above-described process (1). In the process, it is pointed outthat a polyglycerine having reactive hydroxyl groups of 4 to 10 on anaverage is employed as a starting polyglycerine, as a result, aresulting product contains an unreacted polyglycerine, poly-substitutedfatty acid esters such as diester, triester, and tetraester, etc. otherthan the desired fatty acid monoester of a polyglycerine [N. Garti, etal, Journal of American Oil Chemists' Society, 59, 317-319 (1982)].

Furthermore, even in the process (4) in which glycidol is additionpolymerized to a fatty acid monoglyceride, a purity of a reactionproduct remarkably depends upon the starting fatty acid monoglyceride[c.f. U.S. Pat. No. 4,515,775]. Particularly, in the case when there isemployed a fatty acid monoglyceride obtained by the reaction ofglycerine with a fatty acid as a starting material, the startingmaterial contains unreacted glycerine as well as in the above-describedprocess (1), resulting in that a fatty acid monoester of a polyglycerineobtained by the addition polymerization of glycidol contains onlyapproximately 40% of the fatty acid monoester, and the residue ofapproximately 60% is composed of unreacted glycerine andpoly-substituted fatty acid esters [Shigeru Tsuda, Monoglyceride, page67(1985), Maki Book Store].

As described above, there remain a large amount of unreactedpolyglycerine and poly-substituted fatty acid esters in the fatty acidmonoester of a polyglycerine employed until now. In the case when suchthe fatty acid monoester is employed as surfactants or emulsionstabilizers in food industries, it results in decrease of surfacetension, decrease of dispersibility, decrease of foaming ability, anddecrease of stability in emulsifying.

As a process for removing tie unreacted polyglycerine, Japanese PatentUnexamined Publication (Kokai) No. 23837/1988 discloses a process inwhich the unreacted polyglycerine is removed by a liquid separationprocess using a mixed solvent composed of at least one of water-solubleorganic solvents or water and at least one of water-insoluble organicsolvents.

Furthermore, Japanese Patent Unexamined Publication (Kokai) No.81252/1991 discloses a process that the unreacted polyglycerine isremoved by an adsorption method in which a solution of a reactionproduct in esterification is brought into contact with analkyl-silylated silicagel.

Still further, Japanese Patent Unexamined Publication (Kokai) No.41007/1994 discloses an extracting process in which the unreactedpolyglycerine is removed by employing a water-soluble organic solventsuch as n-butyl alcohol, n-propanol, or dioxane, etc. together withwater or an aqueous solution containing a salting agent such as lithium,sodium, potassium or ammonium salts of an organic acid or an inorganicacid such as sulfuric acid or phosphoric acid.

And also, Japanese Patent Unexamined Publication (Kokai) No. 228052/1994discloses an extracting process in which the unreacted polyglycerine isremoved by employing methylethylketone together with water.

However, the process in Japanese Patent Unexamined Publication (Kokai)No. 23837/1988 includes a problem in uses for food-stuff from aviewpoint of safety because of aromatic hydrocarbons such as benzene andtoluene which are described as examples of the water-insoluble organicsolvents. Furthermore, in the process, the reaction molar ratio of afatty acid to a polyglycerine is limited within 1, and there is notdescribed the effectiveness in the reaction molar ratio exceeding 1.

Still further, in the case of a toluene/methanol system, it is observedthat a large amount of a fatty acid ester of polyglycerine having a highHLB value moves to methanol phase containing water even in the reactionratio below 1 and, further, unreacted polyglycerine cannot besufficiently removed, resulting in that there are problems in industrialpreparation.

In addition, the separation process disclosed in the Kokai No.81252/1991 includes disadvantages that operation costs are expensive andoperations are troublesome.

Besides, even though according to the prior arts including the processesdisclosed in the Kokai No. 41007/1994 and 228052/1994, although theunreacted polyglycerine can be removed, poly-substituted esters ofpolyglycerine cannot be removed.

As described hereinabove, in the case when there is prepared a fattyacid esters composition of a polyglycerine according to theabove-described processes (4) and (5) in which glycidol is employed,preparation of polyglycerine can be prevented. However, there is aproblem that a small amount of unreacted glycidol remains in the fattyacid esters composition of a polyglycerine.

Even a small amount, unreacted residual glycidol itself does not exhibitemulsifying ability, and unpreferably causes a remarkable decrease ofsurface tension, dispersibility, foaming ability, and stability inemulsifying in products including the fatty acid esters composition of apolyglycerine.

In order to remove a small amount of unreacted glycidol from thecomposition, there requires molecular distillation which is noteconomical and not preferred from a viewpoint of industrialapplications. It is to be noted that glycidol is another name of anepoxy alcohol.

In view of the above-described background, there has been expected afatty acid esters composition of a polyglycerine containing highcontents of a fatty acid monoester which exhibits an improved surfacetension, dispersibility, foaming ability, and stability in emulsifyingduring uses as an emulsifying stabilizer in the fields of surface activeagents, food-stuffs, cosmetics, and detergents.

Furthermore, the fatty acid esters composition of a polyglycerinecontaining high contents of a fatty acid monoester in the presentinvention effectively acts as a plasticizer, an improver of a wettingability for hydrophobic resins, an improver of a printing property, ananti-static agent, a releasing agent, or an anti-clouding agent, etc.for a variety of resins which include a polyvinyl chloride resin, astyrene-based resin, a methylmethacrylate-based resin, and a polyacetalresin.

For example, a polyvinyl chloride resin has been widely employed as awrapping film or a bottle for food-stuffs, cosmetics, detergents, andother miscellaneous goods, materials for printing such as a calendar anda poster because of its excellent rigidity, transparency, moldability,printing ability.

In particular, uniaxially or biaxially oriented films are employed as ashrinkable wrapping and a shrinkable label because of the excellence inrigidity, a gloss, dimensional stability in storage, and a shrinkableproperty.

However, similarly to other resins, a polyvinyl chloride resin has adisadvantage that static electricity is very readily charged, resultingin that it gives an unpleasant feeling to human bodies and it readilycatches dusts in air.

Accordingly, there is often carried out a process for preventing staticelectricity.

The process for preventing static electricity includes mixing ananti-static agent together with a thermal stabilizer, a reinforcingmaterial, and a slipping agent, etc. in the case of molding a polyvinylchloride resin, or coating an anti-static agent after molding.

As the anti-static agent for vinyl chloride resins, there have beenconventionally employed a fatty acid ester of glycerine, a fatty acidester of sorbitan, a non-ionic surface active agent of a higher alcohol,and an anionic surface active agent such as a sodium alkylbenzenesulfonate and a sodium alkylsulfonate. However, mixing of theanti-static agents cannot sufficiently give an effect for preventingstatic electricity to films having thin thickness such as thermallyshrinkable oriented films, and transparency of the films is occasionallydecreased.

On the other hand, coating of the anti-static agents after molding hasdisadvantages that an effect for preventing static electricity is oftendecreased by rubbing or evaporation with a long lapse of time, andfurther films themselves readily cause blocking.

In JP Kokai No. 1861/1994, although there is disclosed the use of afatty acid esters composition of a polyglycerine for an anti-staticagent, the composition contains a large amount of a residualpolyglycerine and poly-substituted esters, unpreferably resulting inthat an effect for emulsifying and preventing static electricity isremarkably small, whereby, a large amount of the composition has to beemployed.

Meanwhile, a styrene-based resin is excellent in transparency,non-toxic, non-deodorant, and water-resistant.

However, there has been a problem that it is brittle in spite ofexhibiting strength and rigidness. Recently, the brittleness in astyrene-based resin has been improved, whereby, the styrene-based resinhas been used as films for food-stuffs.

Particularly, the styrene-based resin films have a variety of problemsin the use as films for wrapping food-stuffs because of non-affinity forwater.

In the case when the styrene-based resin films are used for wrappingfood-stuffs and stored at low temperatures, moisture in the food-stuffssuch as vegetables or meat forms drops of water over the films. There isa problem that the drops of water adversely affect transparency of thefilms, unpreferably resulting in that the food-stuffs in wrapping cannotbe visually identified, and it is not only visually unpreferred, butalso it gives a bad feeling.

In order to solve the problem, there has been thought out a process forimproving surface properties of the films.

As the process for improving surface properties of the films, there areknown processes that an anti-clouding agent is coated on the films ormixed in preparing the films.

Although the coating process of the anti-clouding agent provides anexcellent anti-clouding effect for a short period after coating,anti-clouding effect becomes decreased by rubbing with a long time oflapse.

On the other hand, the mixing process of the anti-clouding agent canprovide the films with an excellent anti-clouding effect for a longperiod after mixing.

As the anti-clouding agent for the styrene-based resin films, there areknown (1) fatty acid esters of glycerine (JP Kokoku No. 4147/1963 and JPKokoku No. 26532/1977), (2) fatty acid esters of polyethyleneglycol(disclosed in JP Kokoku No. 21112/1964), and (3) fatty acid monoestersof polyglycerine (JP Kokai No. 157558/1986), etc.

However, in the case when the fatty acid esters of glycerine of (1) andthe fatty acid esters of polyethyleneglycol of (2) are employed as theanti-clouding agent for the styrene-based resin films, a large amount ofthose must be employed in order to provide an aimed anti-cloudingeffect, resulting in that mixing is difficult.

In the case when the fatty acid monoesters of polyglycerine of (3) isemployed as the anti-clouding agent for the styrene-based resin films,although an anti-clouding effect at ordinary temperatures is excellent,an anti-clouding effect at low temperatures is poor, and furthermiscibility and transparency are poor, resulting in being notappropriate to wrapping for food-stuffs at low temperatures.

It is to be noted that the fatty acid monoesters of polyglycerine of theabove-described (3) are prepared by the esterification of polyglycerinewith a fatty acid and the purification b y molecular distillation orsolvent extraction, which is different from a fatty acid esterscomposition of polyglycerine in the present invention prepared by theaddition polymerization reaction of glycidol to a fatty acid.

Anti-clouding agent for the styrene-based resin films to be employed forwrapping food-stuffs has to be excellent in a low temperature property,a high temperature property, a recovery property, and durability, etc.Particularly, it attaches importance to an anti-clouding effect at a lowtemperature atmosphere for a long time of period.

In order to make durability of an anti-clouding effect at lowtemperatures exhibit, an anti-clouding agent to be mixed must exhibitmoderate miscibility with the styrene-based resins at low temperatures.

An anti-clouding agent exhibiting a poor miscibility readily moves tothe surface of the film, and it oozes out of the film, unpreferablyresulting in causing blocking of the films in spite of the presence ofthe anti-clouding effect.

On the other hand, an anti-clouding agent exhibiting an excessivemiscibility does not readily move to the surface of the film,unpreferably resulting in not exhibiting the anti-clouding effect.Accordingly, an anti-clouding agent must exhibit a well-balancedmiscibility with resins.

As a conventional anti-clouding agent for the styrene-based resins hasan excessive miscibility with the resins, it is involved inside theresins, resulting in that there has been required a large amount rangingfrom 7 to 8% by weight.

The problems can be solved by the use of the fatty acid esterscomposition of a polyglycerine containing high contents of a fatty acidmonoester in the present invention.

Furthermore, although an article molded from the styrene-based resin isparticularly excellent in transparency, there is a problem that itreadily accumulates static electricity induced by friction, and it doesnot readily disappear, unpreferably resulting in that dust in air isdrawn.

In order to prevent the accumulation of static electricity, surfaceactive agents have been mixed in the resin, or silicone-based compoundshave been coated on the surface of the molded article.

However, there are problems that a small amount of the surface activeagents do not sufficiently provide an anti-static effect and,unpreferably, a large amount of the surface active agents adverselyaffect transparency of the resin, and coating process of silicone-basedcompounds onto the surface of the molded article results in increasingcosts of production.

The problems can be solved by the use of the fatty acid esterscomposition of a polyglycerine containing high contents of a fatty acidmonoester in the present invention.

In the mean time, a methylmethacrylate-based resin is widely employed ina variety of fields which supply parts for automobiles such as a coverfor a variety of meters, optical parts such as photo-magnetic disks andlenses, and a cover for an illuminating lamp, etc., because of itsexcellence in transparency, weatherability, and mechanical properties,etc.

The molded articles are usually prepared by an injection molding and acompression molding. Particularly, the optical parts such asphoto-magnetic disks and lenses are molded by compression molding with aprecise mold, and a molded article is exceedingly tightly in contactwith the mold, whereby, release of the molded article from the moldbecomes insufficient, resulting in making a productivity lower.

Therefore, it is proposed that a variety of releasing agents areemployed in molding a methylmethacrylate-based resin.

For example, JP Kokai No. 73754/1086 discloses a methylmethacrylateresin in which there are mixed higher fatty acid esters, polyvalentalcohols, higher alcohols, higher fatty acids, amides of higher fattyacids, and metal salts of higher fatty acids as releasing agents.

However, a releasing property is insufficient, and the releasing agentsmove to the surface of molded articles, unpreferably resulting in thatthe surface of the mold becomes dirty, and commercial values remarkablydecrease by coloration of the molded article.

The additive which is the fatty acid esters composition of apolyglycerine of the present invention can provide amethylmethacrylate-based resin having an excellent releasing property inspite of a small amount of use.

In the meantime, a polyacetal resin which is one of engineering plasticshas been exceedingly widely employed in a variety of fields which supplyparts for automobiles or home electric appliances, etc., because of itsexcellence in physical properties such as mechanical properties andelectric properties, moldability, and chemical properties such aschemical resistance and thermal stability.

However, as a polyacetal resin unprocessed is poor in a printingproperty by a variety of inks, it has been used after a treatment bycorona discharge.

However, in the case when it is molded, for example, as a shutter for adisk or a magnetic tape cartridge, as the shutter itself is thin inthickness, bending or deformation is unpreferably caused by a long timetreatment or high-voltage treatment in corona discharge, resulting inincapability of practically using.

In view of the situations, there has been expected a material on whichinks can be printed even by a short time treatment or low-voltagetreatment in corona discharge.

Although a process of a primer coating is known as a process forimproving a printing property, the primer process requires solvents,unpreferably resulting in being problematic from viewpoint ofenvironmental pollution.

In JP Kokai No. 195155/1985, there is disclosed a process in which apolyacetal resin is mixed with 0.01-3 parts by weight of hindered aminestogether with 0.01-4 parts by weight of a specific benztriazole-basedultraviolet absorbent in order to improve weatherability.

However, a printing property cannot be sufficiently improved by theprocess, and further, durability of the printing property is almost notimproved.

Furthermore, in JP Kokai No. 128740/1982, there is disclosed a processin which a polyacetal resin is mixed with 0.01-5 parts by weight of afatty acid esters composition of a polyglycerine and/orpolyalkyleneglycol-alkylether.

However, even a printing property cannot be sufficiently improved by theprocess because the fatty acid esters composition of a polyglycerine isnot prepared by the above-described glycidol process (5).

Still further, in JP Kokoku No. 14709/1994, there is disclosed a processin which a polyacetal resin is mixed with 0.01-3% by weight of ahindered amine compound together with an effective amount (as ananti-static agent) a fatty acid ester of a polyvalent alcohol.

However, even a printing property cannot be sufficiently improved by theprocess, and further, durability of the printing property is almost notimproved.

In addition, in JP Kokai No. 41583/1986, there is disclosed a process inwhich a polyacetal resin having the thickness of less than 200 micronsin skin layer.

However, even a printing property cannot also be satisfactorily improvedby the process, and further, durability of the printing property is notoccasionally improved.

The problems in the polyacetal resin can be solved by the use of thefatty acid esters composition of a polyglycerine containing highcontents of a fatty acid monoester in the present invention.

In addition, there is a problem that polyacetal resins or a articlemolded therefrom do not exhibit a sufficient wetting property to waterand a liquid containing water such as water-soluble inks, and blood,etc.

Wide applications of the polyacetal resins demand a variety of specialcharacteristics as materials. One of the special characteristics is animproved wetting property to inks, etc.

Wetting property is prescribed in JIS K6768 in which it is defined as acondition that liquid coated on the surface of a solid is not repelled.

As a method for measuring the wetting property, there is known a methodmeasuring contact angle, and small contact angle represents easiness ofwetting.

Wetting property is required in a variety of molded articles. Forexample, in an ink jet nozzle in a printer for a personal computer,wetting property of the nozzle edge surface is required in order toconstantly control the direction jetting ink, resulting in improvingquality of printing.

Furthermore, in a carrier for a biosensor, improved wetting property ofa sample liquid is required in order to elevate a sensitivity ofmeasurement.

As methods for improving wetting property, there have been put intopractice plasma treatments, chemical treatments, and surface coating bypaints. However, the methods include a disadvantage of inferiorefficiency in production because a highly-controlled technology isrequired in order to guarantee a constant quality in surface treatment.

As methods for improving wetting property in a polyacetal resin,although JP-A-257499/1994 discloses a method in which there is mixed anadditive such as polyethylene glycol for improving wetting property, themethod is insufficient.

Although JP-A-293856/1994 discloses a method in which there is mixed afatty acid esters composition of a polyglycerine for improving wettingproperty, a large amount of the composition must be employed in themethod because a large amount of unreacted polyglycerine remains in thecomposition.

Furthermore, a polyalkyleneglycol or a fatty acid esters composition ofa polyvalent alcohol is also insufficient from viewpoint of improvingwetting property, as shown in Comparative Examples of the presentinvention which are described later.

Still further, a large amount of a compound improving wetting propertyoccasionally tends to adversely affect to mechanical properties andmoldability.

In addition, a polyacetal resin is used as a resin composition by mixinga hindered phenol-based compound, inorganic fibers having short lengthand other additives, in order to prepare small or precise parts havingthin thickness for precision instruments such as a watch, a printer, anda desk top electronic calculator, etc., because of being excellent inmechanical properties and dimensional stability.

As the inorganic fibers having short length, there are exemplifiedfiberglass and fibrous potassium titanate.

However, the fiberglass has the average fiber diameter ranging from 6 to13 microns and the average fiber length ranging from 20 to 3000 microns.Accordingly, diameter and length are too thick and too long, resultingin being incapable of employing, for example, as gears for watch havingthe thickness of 50 or 60 microns.

On the other hand, the fibrous potassium titanate has the average fiberdiameter ranging from 0.2 to 2 microns and the average fiber lengthranging from 10 to 100 microns.

Accordingly, although the fibrous potassium titanate can be employed asthe gears, it often causes a problem of gate plugging in a molding die.

Recently, micro-fibrous titanium oxide has been employed as substitutesfor fiberglass and fibrous potassium titanate.

For example, JP-A-113465/1989 teaches that micro fibrous titanium oxideis employed to prepare a resin composition with which there can beformed molded articles having excellent strength and gloss of thesurface.

However, the polyacetal resin composition in which micro-fibroustitanium oxide is mixed has a drawback that releasing property from amolding die is poor.

The poorness results in a poor profile property of the surface in amolded article and a stain in a molding die.

Particularly, as the molding die for the precise parts is small,cleaning of the stain requires a long maintenance time, resulting infalling productivity.

The problems can be solved by the use of only a small amount of thefatty acid esters composition of a polyglycerine having high contents ofa fatty acid monoester in the present invention.

In the meantime, a fatty acid esters composition of a polyglycerine hasbeen widely used as an additives for cosmetics, toiletries, anddetergents.

As a specific example of cosmetics, a water-in-oil type-emulsifiedcomposition for cosmetics is used as an agent for keeping moisture onhuman skin because outer layer is composed of oil components, resultingin being capable of preventing dryness in the human skin.

It is to be noted that a water-in-oil type-emulsified composition forcosmetics is prepared by mixing a water-soluble high viscous compoundsuch as glycerine, oils and/or waxes, water, and an emulsifier, etc.

As it does not have an affinity to water or sweat, properties are notdiminished by those, preferably resulting in that the properties aredurable for a long time of period.

Furthermore, an affinity to an oily makeup is high, resulting in that itcan be preferably employed as an excellent cleansing for the purpose ofremoving the oily makeup.

However, there are disadvantages that a water-in-oil type-emulsifiedcomposition for cosmetics unpreferably gives an oily or sticky feel whenit is applied on human skin because outer layer is composed of oilcomponents.

In order to solve the disadvantages, a water-in-oil type-emulsifiedcomposition for cosmetics containing a large amount of water has beennumerously investigated, for example, as described in JP-B-26366/1985,JP-A-302935/1988, and JP-A-160709/1994.

However, the water-in-oil type-emulsified composition for cosmeticscontaining a large amount of water is not suitable for the purpose ofremoving the oily makeup because of high content of water. Furthermore,the water-in-oil type-emulsified composition for cosmetics containing alarger amount of water is not thinly extended.

In the JP-A-160709/1994, it is described that a large amount of siliconeoils which are slippery are employed as oil components for outer layerformed by a water-in-oil type-emulsified composition, and furtherviscosity of the composition is controlled within 20000 cps, whereby,thinness and an oily or sticky feel is improved.

Still further, sorbitan fatty acid esters composition or glycerine fattyacid esters composition which is a lipophilic emulsifier has beenemployed in the presence or absence of metal soaps of higher fatty acidsfor preparing the water-in-oil type-emulsified composition forcosmetics. In addition, there are recently employed organiccompound-modified clays composition or mixed emulsifiers containingalpha-monoglyceryl ether.

However, in the case when the composition or emulsifiers are employedwith a large amount of oils, viscosity thereof exceedingly lowers,resulting in that there cannot be readily obtained a water-in-oiltype-emulsified composition for cosmetics having an excellent feel inuse and excellent stability for a long time of period.

Besides, there is described a water-in-oil type-emulsified compositionfor cosmetics having an excellent stability for a long time of period inJP-A-128135/1994 in which a fatty acid esters composition of apolyglycerine is employed. However, the composition is prepared by anesterification reaction of a polyglycerine with a fatty acid which isthe preparation process No. (1) described hereinabove.

As described hereinabove, the composition prepared by an esterificationreaction of a polyglycerine with a fatty acid has problems.

The problems in the water-in-oil type-emulsified composition forcosmetics can be solved by the use of the fatty acid esters compositionof a polyglycerine containing high contents of a fatty acid monoester inthe present invention.

As a specific example of cosmetics, a transparent liquid composition forcosmetics has been used as an agent for keeping moisture on human skin,cosmetics for bathroom, cosmetics for cleansing, cosmetics for amassage, cosmetics for a facial pack, cosmetics for hairs, and a basematerial for medicines, etc.

It is to be noted that a transparent liquid composition for cosmetics isprepared by mixing an non-ionic surface active agent, at least one ofwater-soluble compound having at least two hydroxyl groups, oils, andwater, etc.

The transparent liquid composition for cosmetics usually contains oilycomponents and plasticizers or emulsifiers which are usually non-ionicsurface active agents.

It is known that the non-ionic surface active agents are relatively safefor human skin. Recently, the use of a fatty acid esters composition ofa polyglycerine is proposed similarly to a fatty acid esters compositionof sucrose instead of the non-ionic surface active agents from viewpointof irritating skin.

However, a conventional fatty acid esters composition of polyglycerineis poorer in a solubilizing and emulsifying property compared tonon-ionic surface active agents having polyoxyethylene chains.Particularly, it is difficult to solubilize a large amount of oilycomponents in water which is a base material, and as a composition forcosmetics is highly viscous, there has been a disadvantage that a feelin use is not heavy.

The problems in the transparent liquid composition for cosmetics can besolved by the use of the fatty acid esters composition of apolyglycerine containing high contents of a fatty acid monoester in thepresent invention.

As a specific example of cosmetics, a gel-like emulsified compositionfor cosmetics has been used as cosmetics for cleansing and cosmetics fora massage, etc.

It is to be noted that a gel-like emulsified composition for cosmeticsis usually prepared by mixing glycerine, oils, a polyvalent alcoholexcept glycerine, and an emulsifier, etc.

It has been conventionally difficult to prepare a gel-like emulsifiedcomposition for cosmetics having a stability because of characteristicproperties thereof. In order to prepare a gel-like emulsifiedcomposition having a stability, it has been uncommonly tried to make thecomposition itself high viscous at the sacrifice of a specialcharacteristic and a feel in use.

Furthermore, although a gel-like emulsified composition for cosmeticshas been numerously investigated with development of a hydrophilic fattyacid esters composition of a polyglycerine, there is a problem that aconventional fatty acid esters composition of a polyglycerine exhibitsan unpleasant feel in use which is a poor spreadability because of itssticky property.

As a method for solving the problem, for example, JP-A-224507/1992discloses an instance that there are employed a fatty acid esterscomposition of polyoxyethylenesorbit and/or a fatty acid esterscomposition of polyoxyethyleneglycerine together with a fatty acidesters composition of diglycerine instead of a hydrophilic fatty acidesters composition of a polyglycerine, and JP-A-4911/1993 andJP-A-4912/1993 disclose instances that there are employed naturalsurface active agents.

However, the compositions are insufficient from a viewpoint of safety,there has been expected the development of a fatty acid esterscomposition of a polyglycerine having excellent safety, an excellentfeel in use, and a special characteristic for a gel-like emulsifiedcomposition.

The expectation can be attained by the fatty acid esters composition ofa polyglycerine containing high contents of a fatty acid monoester inthe present invention.

The problems in the gel-like emulsified composition for cosmetics can besolved by the use of the fatty acid esters composition of apolyglycerine containing high contents of a fatty acid monoester in thepresent invention.

As a specific example of cosmetics, a composition for tooth pastecontains a foaming agent in order to give a refreshing feel, adispersing and emulsifying function, and a foaming function, and asurface active agent is employed for giving functions.

It is to be noted that a composition for tooth paste is usually preparedby mixing an abrasive such as secondary hydrated calcium phosphate,water-soluble compounds having high molecular weight such as acarboxymethyl cellulose, a wetting agent such as glycerine, andmedicinal components, etc.

The surface active agent to be employed for giving functions is anessential component. The refreshing feel in teeth-brushing is enhancedby a decrease of surface tension owing to mixing it. Furthermore, theeffect is enhanced by accelerating dispersion and permeation of themedicinal components owing to mixing it. Still further, the surfaceactive agent sensuously gives stability by foaming in use.

As the composition for tooth paste is used in mouth, not only thesurface active agent to be employed must possess excellent ability fordecreasing surface tension and excellent ability for foaming, but alsotaste and odor must be satisfactorily acceptable.

Therefore, there have been conventionally employed anion surface activeagents not having taste and odor such as a sodium alkylsulphate, sodiumacylsalkosinate, alpha-olefin sulphonate, and a monoglyceride composedof sodium sulphate and a coconut oil, etc.

However, the anionic surface active agents have disadvantages thatmucous membrane in mouth is irritated, tastes of foods are changed afterusing, and an effect by enzymes to be mixed as medicinal components intooth paste is decreased. Furthermore, safeness has recently becomeproblematic.

In view of situations, anionic surface active agents have advantages ofmilder irritation to skin and mucous membrane compared to anionicsurface active agents. Furthermore, the anionic surface active agentshave an advantage of not decreasing the effect by enzymes, and a fattyacid esters composition of sucrose and a fatty acid esters compositionof a polyglycerine are narrowly approved as surface active agents forfood processing.

Therefore, a fatty acid esters composition of sucrose and a fatty acidesters composition of a polyglycerine are proposed as surface activeagents for mixing in tooth paste.

However, a fatty acid esters composition of sucrose and a conventionalfatty acid esters composition of a polyglycerine have disadvantages thatthose do not sufficiently foam in use, and an effect as tooth paste anda feel in use are exceedingly poor. It is only known that monolaurate ofsucrose and monomyristate of sucrose were mixed [G. L. Fosol and P.Rovesti, (International Symposium on Sugar-ester) Maison de la ChimieParis, Jun. 8, 1960].

The problems in the composition for tooth paste can be solved by the useof the fatty acid esters composition of a polyglycerine containing highcontents of a fatty acid monoester in the present invention.

As a specific example of cosmetics, a cleaning agent composition iswidely used in a variety of fields. Particularly, a cleaning agentcomposition importantly acts in food industries,

In the food industries, it is used for cleaning foods themselves,starting materials for foods processing, apparatuses for foodsprocessing, and containers such as bottles or cans.

In the food industries, safeness of a cleaning agent composition isseverely demanded because it possibly remains in apparatuses,containers, and foods themselves to be cleaned, resulting in that it istaken together with foods or beverages in human body.

Particularly, as a cleaning agent composition for the food industries isoften used for foods themselves, there have been used a fatty acidesters composition of sucrose and a fatty acid esters composition ofglycerine which are also additives for foods from viewpoint of safeness(Journal of Food Sanitation, vol. 18, No. 3, page 217).

Furthermore, JP-A-158090/1994 discloses that there is used a mixturecomposed of a monoglyceride composition of a polycarboxylic acid esterand a fatty acid esters composition of glycerine which are ionic surfaceactive agents as a cleaning agent composition. However, the cleaningagent composition in the Journal and the mixture in the JP are notsufficient in cleaning ability.

The problems in the cleaning agent composition can be solved by the useof the fatty acid esters composition of a polyglycerine containing highcontents of a fatty acid monoester in the present invention.

The cleaning agent composition of the present invention is harmless forhuman body and strong in cleaning ability, and it can be preferably usedas a cleaning agent composition for foods, starting materials for foods,apparatuses for foods processing, and bottles, containers, and cans infood industries.

As a specific example of cosmetics, a foaming composition for cleaningis widely used as a cleaning agent in cosmetic fields and a detergentfor a kitchen or bathroom.

For example, hair washing with a shampoo requires rinsing by water orwarmed water after washing. However, in the case when a person cannothave a bath or cannot wash with water because of an injury, or in aplace being incapable of using water, it is difficult to clean hair.

Therefore, there is proposed a wiping type cleaning agent which does notrequire rinsing.

Specifically, there are exemplified an aerosol type water-based cleaningcomposition in JP-B-47960/1982, a foaming hair cleaning agent inJP-A-289023/1986, a foaming hair cleaning agent for wiping a shampoo inJP-A-205011/1987, a dry hair cleaning method and an agent therefor inJP-A-14711/1988, and an aerosol type shampoo composition inJP-A-190813/1988, etc.

However, conventional compositions in which an electrolyte-based surfaceactive agent is employed are not sufficient in stimulation to head skinand hair by only wiping, and spray-type conventional compositions inwhich a non-electrolyte-based surface active agent is employed are notsatisfied because cleaning agents are scattered beyond necessaryportions, and foam-type conventional compositions in which anon-electrolyte-based surface active agent is employed are not satisfiedin cleaning ability and refreshing feeling because a mixing amount ofalcohols is limited in order to prepare a foam type one.

Furthermore, JP-A-100435/1994 discloses that a non-electrolyte-basedsurface active agent such as a fatty acid esters composition of apolyglycerine is employed in combination with a higher alcohol toprepare a foaming composition for cleaning containing a large amount ofthe higher alcohol.

However, the conventional fatty acid esters composition of apolyglycerine is not prepared by the glycidol process (5) as describedhereinabove. Accordingly, the content of a fatty acid monoester is lowin the composition, resulting in that the foaming composition forcleaning does not satisfactorily exhibit sufficient stability for a longtime of period, a cleaning effect, and a refreshing feel.

The problems in the foaming composition for cleaning can be solved bythe use of the fatty acid esters composition of a polyglycerinecontaining high contents of a fatty acid monoester in the presentinvention.

As a result of an intensive investigation by the present inventors, thepresent invention has been completed.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a fatty acid esterscomposition of a polyglycerine containing more than 70% of a fatty acidmonoester and a process for the preparation thereof.

It is another object of the present invention to provide ahighly-purified fatty acid esters composition of a polyglycerine and aprocess for the preparation thereof.

It is other object of the present invention to provide the use of afatty acid esters composition of a polyglycerine as an additive forfood-stuffs, thermoplastic resins, cosmetics, and detergents.

A first aspect of the present invention relates to a fatty acid esterscomposition of a polyglycerine containing more than 70% of a fatty acidmonoester represented by general formula [1]described below;

RCO—[OCH₂CH(OH)CH₂]_(n)—OH  [1]

wherein R is an alkyl group, an alkenyl group, or a hydroxylgroup-substituted alkyl group which have a carbon number ranging from 6to 21, and n is an integer of at least 4, based on a peak area ratiodetected using an ultraviolet ray absorption detector in a highperformance liquid chromatographic analysis method.

A second aspect of the present invention relates to a process for thepreparation of a fatty acid esters composition of a polyglycerine whichcomprises the reaction of a fatty acid represented by general formula[2] described below;

RCOOH  [2]

wherein R is an alkyl group, an alkenyl group, or a hydroxylgroup-substituted alkyl group which have a carbon number ranging from 6to 21, with glycidol in the presence of a phosphoric acid-based acidiccatalyst.

A third aspect of the present invention relates to a process for thepreparation of a highly-purified fatty acid esters composition of apolyglycerine which comprises the steps;

(a) allowing to react a fatty acid with glycidol to obtain a fatty acidesters composition of a polyglycerine,

(b) removing water after adding water into said fatty acid esterscomposition of a polyglycerine, and then heating.

A fourth aspect of the present invention relates to a highly-purifiedfatty acid esters composition of a polyglycerine having an oxiraneoxygen concentration of below 100 ppm, said oxirane oxygen concentrationis defined by the titration method defined in Cd. 9-57 of Journal ofAmerican Oil Chemists' Society, or having a ratio of below 0.01%, saidratio is a peak area value of a chemical shift between 2.7 ppm and 2.8ppm assigned by methylene proton derived from an oxirane group withrespect to a peak area value of a chemical shift between 3.4 ppm and 4.4ppm assigned by methylene proton and methine proton derived from apolyglycerine with a proton NMR.

A fifth aspect of the present invention relates to the use of a fattyacid esters composition of a polyglycerine in the first aspect or ahighly-purified fatty acid esters composition of a polyglycerine in thefourth aspect for an additive for food-stuffs.

A sixth aspect of the present invention relates to a resin compositionwhich comprises a fatty acid esters composition of a polyglycerine inthe first aspect or a highly-purified fatty acid esters composition of apolyglycerine in the fourth aspect, and a thermoplastic resin.

A seventh aspect of the present invention relates to a water-in-oiltype-emulsified composition for cosmetics which comprises glycerine,oils and/or waxes, water, and a fatty acid esters composition of apolyglycerine in the first aspect or a highly-purified fatty acid esterscomposition of a polyglycerine in the fourth aspect.

An eighth aspect of the present invention relates to a transparentliquid composition for a cleansing which comprises at least one of annon-ionic surface active agent, at least one of water-soluble compoundhaving at least two hydroxyl groups, oily components, water, and a fattyacid esters composition of a polyglycerine in the first aspect or ahighly-purified fatty acid esters composition of a polyglycerine in thefourth aspect. a highly-purified fatty acid esters composition of apolyglycerine in the fourth aspect or a highly-purified fatty acidesters composition of a polyglycerine in the fourth aspect, and an agentfor spraying said mixture.

A ninth aspect of the present invention relates to a gel-like emulsifiedcomposition for cosmetics which comprises glycerine, liquid oilycomponents, a polyvalent alcohol except glycerine, and a fatty acidesters composition of a polyglycerine in the first aspect or ahighly-purified fatty acid esters composition of a polyglycerine in thefourth aspect.

A tenth aspect of the present invention relates to a composition fortooth paste which comprises an abrasive, a caking material, a wettingagent, and a fatty acid esters composition of a polyglycerine in thefirst aspect or a highly-purified fatty acid esters composition of apolyglycerine in the fourth aspect.

An eleventh aspect of the present invention relates to a cleaning agentcomposition which comprises (a) a polycarboxylic acid ester of amonoglyceride or a salt thereof represented by general formula [3]

R1—COO—CH₂—CHOZ1—CH₂OZ2  [3]

wherein R1 is an alkyl or alkenyl group having a carbon number rangingfrom 7 to 17, either Z1 or Z2 is a residual group of a polycarboxylicacid or salt thereof, and another hydrogen atom or a residual group of apolycarboxylic acid or salt thereof, (b) a fatty acid esters compositionof a polyglycerine as set forth in claim 1 or a highly-purified fattyacid esters composition of a polyglycerine as set forth in claim 14, (c)organic or inorganic builders, (d) fluidity improvers, and additionally(e) thickening agents, (f) perfumes, (g) coloring agents, (h)sterilizers, (i) enzymes, and (j) anti-inflammatory agents.

A twelfth aspect of the present invention relates to a foamingcomposition for cleaning which comprises a mixture composed of at leastone of a lower monovalent alcohol having a carbon number ranging from 1to 3, water, at least one of a higher alcohol having a carbon numberranging from 12 to 22, and a fatty acid esters composition of apolyglycerine in the first aspect or a highly-purified fatty acid esterscomposition of a polyglycerine in the fourth aspect.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart obtained by a high performance liquid chromatographyanalysis (HPLC) relating to a lauric acid esters composition of apolyglycerine obtained in Example 1.

FIG. 2 is a chart obtained by HPLC relating to a lauric acid esterscomposition of a polyglycerine obtained in Example 2.

FIG. 3 is a chart obtained by HPLC relating to a lauric acid esterscomposition of a polyglycerine obtained in Example 3.

FIG. 4 is a chart obtained by HPLC relating to a lauric acid esterscomposition of a polyglycerine obtained in Example 4.

FIG. 5 is a chart obtained by HPLC relating to a lauric acid esterscomposition of a polyglycerine obtained in Example 5.

FIG. 6 is a chart obtained by HPLC relating to a lauric acid esterscomposition of a polyglycerine obtained in Comparative Example 1.

FIG. 7 is a chart obtained by HPLC relating to a lauric acid esterscomposition of a polyglycerine obtained in Comparative Example 2.

FIG. 8 is a chart obtained by HPLC relating to a lauric acid esterscomposition of a polyglycerine obtained in Comparative Example 3.

FIG. 9 is a chart obtained by HPLC relating to a lauric acid esterscomposition of a polyglycerine obtained in Comparative Example 4.

FIG. 10 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 5.

FIG. 11 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 6.

FIG. 12 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 7.

FIG. 13 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 8.

FIG. 14 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 9.

FIG. 15 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 10.

FIG. 16 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 11.

FIG. 17 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 12.

FIG. 18 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 13.

FIG. 19 is a chart obtained by HPLC relating to commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 14.

FIGS. 20 and 21 (enlarged chart of 20) are a proton NMR chart relatingto the product obtained in Example 6 (first step).

FIGS. 22 and 23 are a proton NMR chart relating to the product obtainedin Example 6 (second step).

FIG. 24 is a chart obtained by HPLC relating to PGMLEC obtained inExample 28.

FIG. 25 is a chart obtained by HPLC relating to a commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 16.

FIG. 26 is a chart obtained by HPLC relating to a commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 17.

FIG. 27 is a chart obtained by HPLC relating to a commercially suppliedfatty acid esters composition of a polyglycerine employed in ComparativeExample 18.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be described hereinafter in more detail.

According to a first aspect of the present invention, there is provideda fatty acid esters composition of a polyglycerine containing more than70% of a fatty acid monoester represented by general formula [1]described below;

RCO—[OCH₂CH(OH)CH₂]_(n)—OH  [1]

wherein R is an alkyl group, an alkenyl group, or a hydroxylgroup-substituted alkyl group which have a carbon number ranging from 6to 21, and n is an integer of at least 4, based on a peak area ratiodetected using an ultraviolet ray absorption detector in a highperformance liquid chromatographic analysis method.

According to a second aspect of the present invention, there is provideda process for the preparation of a fatty acid esters composition of apolyglycerine which comprises the reaction of a fatty acid representedby general formula [2] described below;

RCOOH  [2]

wherein R is an alkyl group, an alkenyl group, or a hydroxylgroup-substituted alkyl group which have a carbon number ranging from 6to 21, with glycidol in the presence of a phosphoric acid-based acidiccatalyst.

The fatty acid esters composition of a polyglycerine containing morethan 70% of a fatty acid monoester represented by the general formula[1] of the first aspect of the present invention can be prepared by theprocess of the second aspect of the present invention.

As the fatty acid represented by the general formula [2], there areemployed fatty acids having a carbon number ranging from 7 to 22 whichmay be a saturated or unsaturated acid, a linear aliphatic or branchedacid and, further a substituted fatty acid in which hydroxyl groups aresubstituted for carbon chains. As an example of the fatty acids, thereare specifically exemplified caproic acid, caprylic acid,2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid,myristic acid, palmitic acid, palmitoreic acid, stearic acid, isostearicacid, oleic acid, linoleic acid, behenic acid, erucic acid, licinoleicacid, hydroxystearic acid, etc., which may be employed solely or incombination. The fatty acid may be employed solely or in combination.

It is to be noted that glycidol is another name of an epoxy alcoholwhich has the chemical structure of

The fatty acid is allowed to react with glycidol in the presence of aphosphoric acid-based acidic catalyst.

The phosphoric acid-based acidic catalyst to be essentially employed inthe present invention includes phosphoric acids or esters thereof.Specifically, there are exemplified phosphoric acids such as phosphoricacid, phosphoric anhydride, polyphosphoric acid, orthophosphoric acid,metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, andtetraphosphoric acid, acidic esters of phosphoric acid such as methylacid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butylacid phosphate, and 2-ethylhexyl acid phosphate, etc.

Furthermore, there can be also employed monoester compound, diestercompound, and an admixture thereof. Of those, phosphoric acid and acidicesters of phosphoric acid are preferably employed. The catalyst may beemployed solely or in combination.

The catalysts are employed in an amount ranging from 0.01 to 10% byweight, preferably from 0.1 to 5% by weight based on the fatty acid.

In the case when the amount is below 0.01% by weight, the reaction rateis low and, on the contrary, even in the case when the amount exceeds10% by weight, the reaction rate is not promoted and, it is not onlymeaningless, but also addition polymers of glycidol itself unpreferablyby-produce depending upon the catalysts which act as initiators.

The reaction is carried out by charging the fatty acid into a reactionvessel and adding the catalyst, followed by gradually adding glycidol.The reaction is carried out in temperatures ranging from 50 to 180° C.,preferably from 70 to 160°°C., and more preferably from 120 to 140° C.

In the case when the temperature is below 50° C., the reaction rate isslow and, on the contrary, in the case when it exceeds 180° C., productsremarkably color, and in the case of exceeding 230° C., glycidoldecomposes and side reactions are unpreferably caused. In order toprevent elevation of the temperatures, there can be employed a solventhaving a low-boiling point which is inert to glycidol.

Furthermore, the reaction is preferably carried out under a nitrogen gasatmosphere which may be optionally pressurized.

The reaction may be carried out by a batch type or continuous typeprocess.

The reaction molar ratio of glycidol to the fatty acid ranges from 1 to100, preferably from 1 to 50 and, more preferably from 1 to 10.

In the case when the ratio is below 1, the fatty acid unreactedunpreferably remains in a reaction product and, on the contrary, in thecase when the ratio exceeds below 100, there cannot be obtained adesired fatty acid esters composition of a polyglycerine.

Although solvents may be employed in the reaction, it is preferred thatsolvents are not employed in the use as additives for foods.

Examples of the solvents include an aromatic hydrocarbon such asbenzene, toluene, and xylene, a halogenated toluene such astrifluorotoluene, an aliphatic ketone having a carbon number rangingfrom 3 to 9 such as methylisopropyl ketone, methylisobutylketone,diethylketone, and diisobutylketone, etc.

Furthermore, there can be employed ethers such as diisopropylether, etc.The solvent may be employed solely or in combination. In the case whenthe solvent is employed, it is employed in an amount of 2 times byweight at most based on the total weight of starting materials.

According to the above-described process, there can be obtained a fattyacid esters composition of a polyglycerine having a high polymerizationdegree. The fatty acid esters composition of a polyglycerine is anadmixture composed of a monoester compound, a diester compound, and atriester compound.

The fatty acid esters composition of a polyglycerine of the presentinvention contains more than 70% of a fatty acid monoester representedby the general formula [1] described hereinabove.

In order to define the content of a fatty acid monoester compound in afatty acid esters composition of a polyglycerine, there is employed ahigh performance liquid chromatographic analysis method (hereinafter,referred to as HPLC).

In the HPLC analysis method, a peak area ratio is detected using anultraviolet (UV) ray absorption detector. The analytical condition maybe selected from the following three conditions.

Analytical condition No. 1:

Column: 2 pieces (connected in series) of Wakosil 5C18 manufactured byWako Jun-yaku Ltd. or equivalent, which is a reversed phase distributioncolumn (an ODS column) having an octadecyl group as a functional group

Column size; 4.6 mm phi×250 mmL

Eluent for development; Methanol

Flow rate of the eluent; 0.05 to 1.0 ml/min (eg. 0.75 ml/min)

Column oven temperature; 30 to 60° C. (eg. 40° C.)

Wave length in UV ray absorption detector; 210 nm

Sample concentration; 1 to 50% (eg. 5% in methanol solution)

Sample volume; 0.1 to 20 micro liter (eg. 5 micro liter)

Retention time of polyglycerine; 8 minutes

Retention time of monoester compound; 8-12 minutes

Retention time of other ester compounds; >12 minutes

Retention time of methanol; exceeding 18 minutes

Analytical condition No. 2:

Column; Wakosil II 5C18HG manufactured by Wako Jun-yaku Ltd. orequivalent, which is a reversed phase distribution column (an ODScolumn) having an octadecyl group as a functional group

Column size; 4.6 mm phi×250 mmL

Eluent for development; Methanol

Flow rate of the eluent; 0.05 to 1.0 ml/min (eg. 0.20 ml/min)

Column oven temperature; 30 to 60° C. (eg. 40° C.)

Wave length in UV ray absorption detector; 210 nm

Sample concentration; 1 to 50% (eg. 10% in methanol

Sample volume; 0.1 to 20 micro liter (eg. 10 micro liter)

Retention time of polyglycerine; before 14 minutes

Retention time of monoester compound; 14-16.5 minutes

Retention time of other ester compounds; >16.5 minutes

Retention time of methanol; exceeding 18 minutes

Analytical condition No. 3:

Column; Wakosil 5C18 and Wakosil II 5C18HG (connected in series)manufactured by Wako Jun-yaku Ltd. or equivalent, which is a reversedphase distribution column (an ODS column) having an octadecyl group as afunctional group

Column size; 4.6 mm phi×250 mmL

Eluent for development; Ethanol

Flow rate of the eluent; 0.05 to 1.0 ml/minute (eg. 0.20 ml/min)

Column oven temperature; 30 to 60° C. (eg. 40° C.)

Wave length in UV ray absorption detector; 210 nm

Sample concentration; 1 to 50% (eg. 5% in ethanol solution)

Sample volume; 0.1 to 20 micro liter (eg. 10 micro liter)

Retention time of polyglycerine; below 28.5 minutes

Retention time of monoester compound; 28.5-34 minutes

Retention time of other ester compounds; exceeding 34 minutes

Retention time of ethanol; 39 minutes

As an eluent for development, there can be preferably employed analcohol and a mixture composed of alcohol/water.

The eluent for development is selected depending upon the kind of afatty acid of which a fatty acid esters composition of a polyglycerineis composed, and depending upon the amount of glycidol introduced. Forexample, in the case when a lauric acid esters composition of apolyglycerine is analyzed, methanol is preferably employed as theeluent, and in the case when a stearic acid esters composition of apolyglycerine is analyzed, ethanol is preferably employed as the eluent.

Samples (as a solution of an eluent for development) in the HPLCanalysis method are employed in an amount ranging from 0.1 to 20 microliter, preferably from 5 to 10 micro liter depending upon the solubilityof samples into the eluent and the kind of samples. Sample concentrationranges from 1 to 50%, preferably from 5 to 10% in the eluent.

In separation by the HPLC analysis method using a column (an ODS column)having an octadecyl group, no-substituted polyglycerine components whichhave a higher polarity are firstly detected, and then fatty acid esterscomponents of a polyglycerine are detected.

In the fatty acid esters components, monoester compound is firstlydetected, and then diester compound is detected, and further other ester(triester, tetraester, . . . ) compounds are detected. The content ofthe monoester compound is calculated according to the followingequation.

Content of a monoester compound=[A/(B−C)]×100(%)

A: peak area from the beginning in detection of fatty acid esters of apolyglycerine to detection of fatty acid monoester compound

B: total peak area of all components

C: peak area of solvent

Speaking of peak area by a solvent, it is to be noted that it isimportant to select a solvent so that a retention time by the solventdoes not overlap retention time by other components.

The above-described equation for calculating the content of a monoestercompound is based on the premise that a retention time by the solvent ispresent before retention time by other components.

There may be optionally refined the fatty acid esters composition of apolyglycerine containing more than 70% of a fatty acid monoester of thepresent invention.

As methods for refining, there are exemplified:

(1) A method for removing odor by a steam injection process in whichsaturated steam is blown at reduced pressures.

(2) A method for decoloration by a bleaching process using sodiumhypophosphate or hydrogen peroxide.

According to a third aspect of the present invention, there is provideda process for the preparation of a highly-purified fatty acid esterscomposition of a polyglycerine which comprises the steps;

(a) allowing to react a fatty acid with glycidol to obtain a fatty acidesters composition of a polyglycerine,

(b) removing water after adding water into said fatty acid esterscomposition of a polyglycerine, and then heating.

The highly-purified fatty acid esters composition of a polyglycerine ofthe present invention is prepared by the two steps (a) and (b).

The step (a) corresponds to the above-described reaction process in thesecond aspect of the present invention.

A product obtained in the step (a) corresponds to the above-describedfatty acid esters composition of a polyglycerine in the first aspect ofthe present invention.

It is to be noted that the fatty acid esters composition of apolyglycerine obtained in the step (a) usually contains oxirane oxygenranging from 500 to 2000 ppm based on a titration method describedhereinafter.

The step (b) is described below in detail.

In the step (b), water is added into the fatty acid esters compositionof a polyglycerine obtained in the step (a), and then the composition isheated, followed by removing water.

In the step (b), water is added in an amount ranging from 0.1 to 20% byweight, and preferably from 1 to 10% by weight based on the weight ofthe above-described fatty acid esters composition of a polyglycerine.

In the case when the amount of water is below 0.1%, unreacted glycidolcannot be sufficiently decreased and, on the contrary, in the case whenthe amount of water exceeds 20%, it unpreferably requires a long time ofperiod for removing water.

Unreacted glycidol is changed to glycerine by heating after addingwater. Heating temperature in the step (b) ranges from 60 to 200° C.,and preferably from 80 to 160° C.

In the case when the temperature is below 60° C., unreacted glycidolcannot be sufficiently decreased and, on the contrary, in the case whenthe temperature exceeds 200° C., there unpreferably colors the fattyacid esters composition of a polyglycerine.

Heating time of period ranges from 0.5 to 15 hours, and preferably from1 to 7 hours depending upon heating temperatures.

In the case when the heating time is below 0.5 hour, glycidol cannot besufficiently decreased and, on the contrary, in the case when the timeexceeds 15 hours, there unpreferably colors the fatty acid esterscomposition of a polyglycerine.

In the step (b), water is removed after the completion of heating toobtain the fatty acid esters composition of a polyglycerine notcontaining unreacted glycidol.

Water can be removed by distillation, azeotropic distillation, anddistillation under reduced pressures.

Heating temperatures in distillation ranges from 100 to 200° C., andpreferably from 110 to 160° C.

In the case when the distillation temperature is below 100° C., watercannot be sufficiently removed and, on the contrary, in the case whenthe temperature exceeds 200° C., there unpreferably colors the fattyacid esters composition of a polyglycerine.

Distillation time of period ranges from 1 to 10 hours, and preferablyfrom 1 to 6 hours depending upon temperatures and the degree of reducedpressures in distillation.

In the case when the distillation time is below 1 hour, water cannot besufficiently removed and, on the contrary, in the case when the timeexceeds 10 hours, there unpreferably colors the fatty acid esterscomposition of a polyglycerine.

In the case when a solvent is employed in the step (a), it can beremoved in the distillation together with water.

According to a fourth aspect of the present invention, there is provideda highly-purified fatty acid esters composition of a polyglycerinehaving an oxirane oxygen concentration of below 100 ppm, said oxiraneoxygen concentration is defined by the titration method defined in Cd.9-57 of Journal of American Oil Chemists' Society, or having a ratio ofbelow 0.01%, said ratio is a peak area value of a chemical shift between2.7 ppm and 2.8 ppm assigned by methylene proton derived from an oxiranegroup with respect to a peak area value of a chemical shift between 3.4ppm and 4.4 ppm assigned by methylene proton and methine proton derivedfrom a polyglycerine with a proton NMR.

In order to determine the concentration value of oxirane oxygen in thehighly purified fatty acid esters composition of a polyglycerine of thefourth aspect, there is employed the titration method defined in Cd.9-57 of Journal of American Oil Chemists' Society, (Journal of AmericanOil Chemists' Society, 41, 86-87 (1964)) or having a ratio of below0.01%, said ratio is a peak area value of a chemical shift between 2.7ppm and 2.8 ppm assigned by methylene proton derived from an oxiranegroup with respect to a peak area value of a chemical shift between 3.4ppm and 4.4 ppm assigned by methylene proton and methine proton derivedfrom a polyglycerine with a proton NMR.

The titration method defined in the tentative method Cd. 9-57, OxiraneOxygen by D. S. Bolly et al and cited in the Journal of American OilChemists' Society Volume 41, pp. 86-87 (1964) is a method for measuringoxirane oxygen which is described below.

Definition: This method determines oxirane oxygen which is the oxygencontained in the following grouping:

Under the prescribed conditions of this method, the oxygen is titrateddirectly with hydrogen bromide in acetic acid.

Scope: Applicable to epoxidized fatty materials and epoxy compounds ingeneral.

A. Apparatus:

1. Buret assembly of the Machlette type (gravity feed), available fromScientific Glass Apparatus Co. Cat. No. JB6715 or equivalent. Provide aclosed system for titration to avoid loss of hydrogen bromide attachingthe titration flask to the buret tip with a one-hole rubber stopper. Thehole in the stopper should be formed so as to take the buret tip snuglywith a small side opening to permit air to escape from the flask duringtitration.

2. Flask: Erlenmeyer, 50 ml,

3. A magnetic stirrer of any suitable type with round magnetic stirringbars covered with “Teflon” or equivalent protective covering.

B. Reagents:

1. Glacial acetic acid, A.C.S. grade, acetic anhydride free

2. Hydrogen bromide gas, anhydrous, available in cylinders from MathesonCompany, Inc., Joliet, Ill. or 30-32% hydrogen bromide in acetic acidavailable from Eastman Kodak Co.

3. Crystal violet (Gentian violet), Eastman Kodak No. 1350 orequivalent.

4. Acid potassium Phthalate, National Bureau of Standard, Standard forAcidimetry. Dry for two hours at 120° C. and allow to cool in anefficient desiccator prior to use.

5. Benzene, A.C.S. grade or chlorobenzene, analytical reagent grade.

C. Solutions:

1. Crystal violet indicator soln. ; dissolve 0.1 g. of crystal violet in100 ml. of glacial acetic acid.

2. Hydrogen bromide 0.1 N in acetic acid.

a. Prepare by bubbling hydrogen bromide gas through glacial acetic acidto approximately 0.1N. A torsion type balance may be use to estimate theamount of hydrogen bromide added.

b. or, prepare by diluting 30 to 32% (about 4N) hydrogen bromide inacetic acid with glacial acetic acid to approximately 0.1N.

Standardization: Weigh accurately about 0.4 g. of dry acid potassiumphthalate and dissolve in 10 ml. glacial acetic acid. Heat carefullydissolve, using a hot plate. Titration solution at room temperature withhydrogen bromide using no more than 0.1 ml. (5 drops from a finedropper) of crystal violet indicator. Standardization should be induplicate with a difference not to exceed 0.0004 N. Restandardize eachday samples are analyzed.

Normality=(Weigh of Phthalate)/(0.2042×Titration)

D. Procedure:

1. Weigh 0.3-0.5 g. (plus or minus 0.0001 g.) of the sample into a 50ml. Erlenmeyer flask. Dissolve the sample in 10 ml of benzene orchlorobenzene (in case of epoxy resins use chlorobenzene). Add stirringbar and crystal violet indicator (maximum 0.1 ml. or 5 drops with a finedropper).

2. Place the rubber stopper in position and lower the tip of the buretuntil it discharges just above the solution.

3. Stir and titrate the sample (rapidly at first) with the 0.1 Nhydrogen bromide solution to a bluish-green end point that persists for30 seconds. Control the rate of the magnetic stirrer so as to avoidsplashing.

E. Calculation:

Oxirane Oxygen, %=(Titration×N×1.60)/(Weight of sample)

F. Responsibility:

The average variance of components calculated from the collaborativedata obtained by the investigating Committee indicate the following 95%probability limits:

1. The difference between duplicate determinations made within alaboratory should not exceed . . . 0.8

2. The difference between the average or duplicate determinations madein different laboratories should not exceed . . . 0.19

G. Note:

1. This method is not applicable to oils containing alpha andbeta-unsaturated ketones, cyclopropenes-conjugated dienols, oxidizedfats, and soaps.

2. Long standing has a deleterious effect on hydrogen bromide solutionsand should be avoided.

In the proton NMR method in order to determine the concentration valueof oxirane oxygen in the highly purified fatty acid esters compositionof a polyglycerine, methane-deuterium chloride is employed as a solvent,the solution concentration of the fatty acid esters composition of apolyglycerine is approximately 5%, temperature for measuring is 40° C.plus or minus 0.5° C., and JOEL270Mz (manufactured by Nihon Denshi,Ltd.) or equivalent is employed as an NMR apparatus.

Although starting materials for the highly-purified fatty acid esterscomposition of a polyglycerine having an oxirane oxygen concentration ofbelow 100 ppm or having the ratio of below 0.01% can be obtained by theprocess of the above-described second aspect or the step (a) in thethird aspect, preparation processes thereof are not particularlylimited.

Starting materials for the highly-purified fatty acid esters compositionof a polyglycerine having an oxirane oxygen concentration of below 100ppm or having the ratio of below 0.01% may also be provided by any oneof the above-described preparation processes, that is, (1) anesterification reaction of a polyglycerine with a fatty acid, (2) atransesterification reaction of a polyglycerine with a fatty acid ester,(3) a transesterification reaction of a polyglycerine with an oil andfatty acid, (4) an addition polymerization reaction of glycidol to amonoglyceride of a fatty acid including (5) an addition polymerizationreaction of glycidol to a fatty acid, etc.

The starting materials for the highly-purified fatty acid esterscomposition of a polyglycerine contain an oxirane oxygen ranging from100 to 2000 ppm which is measured by the titration method defined in theCd. 9-57 of Journal of American Oil Chemists' Society.

According to a fifth aspect of the present invention, there is providedthe use of a fatty acid esters composition of a polyglycerine in thefirst aspect or a highly-purified fatty acid esters composition of aPolyglycerine in the fourth aspect for an additive for food-stuffs.

As examples of the food-stuffs to be applied, there are specificallyexemplified a material for drinks such as a cacao, coffee, and tea, astarch-based product such as noodles, kneaded bread-stuffs or bread,cookies, and cake, a dairy product such as a milk fermented by lacticacid, butter, and cheese, processed meat or processed fish meat, and anoils&fats composition which is composed of vegetable oils and/orhydrogenated animal or fish oils and other additives, etc.

As an additive for a variety of tile food-stuffs, the fatty acid esterscomposition of a polyglycerine in the first or fourth aspect is employedin an amount ranging from 0.01% to 5% by weight, preferably from 0.05 to2% by weight, and more preferably from 0.1 to 1% by weight based on thetotal amount of the food-stuffs including water, although it dependsupon the kind of the food-stuffs.

In the case when the amount is below 0.01%, effect by the use ismeaninglessly small and, on the contrary, in the case when the amountexceeds 5%, a taste or flavor inherently possessed in the food-stuffs isadversely affected.

The fatty acid esters composition of a polyglycerine acts as astabilizer for emulsifying, an emulsifier or an accelerator thereof, asurface active agent, a dispersant, a binder, or a plasticizer for avariety of food-stuffs.

Effect by the use of the fatty acid esters composition of apolyglycerine is more specifically described below relating torespective food-stuffs.

In the case when the fatty acid esters composition of a polyglycerine ofthe present invention is employed in kneaded bread-stuffs, fermentationby yeast for bread is stabilized for long time of period even withoutcontrolling temperatures, resulting in that there can be prepared breadhaving an excellent taste.

For the kneaded bread-stuffs which are one of the starch-based product,the fatty acid esters composition of a polyglycerine is employed in anamount of less than 0.5% by weight together with other additives such asapproximately 0.1% by weight of calcium carbonate, approximately 0.1% byweight of powdered egg white, and a small amount of salt, seasoning, andflavors, etc. based on flour. Fermentation by yeast for bread of thekneaded bread-stuffs is carried out at temperatures of 25 to 30° C. for10 to 24 hours.

For noodles which are one of the starch-based products, the fatty acidesters composition of a polyglycerine is employed in an amount rangingfrom 0.1 to 0.5% by weight based on the weight of flour together withother additives such as salt and egg white, etc.

In the case when the fatty acid esters composition of a polyglycerine ofthe present invention is employed in noodles, it acts as a surfaceactive agent, resulting in that adhering of noodles itself can beprevented.

In the case when the fatty acid esters composition of a polyglycerine ofthe present invention is employed in the dairy product, it acts as adispersant or an emulsifier, resulting in that separation of fats can beprevented.

For the milk fermented by lactic acid which is one of the dairy product,the fatty acid esters composition of a polyglycerine is employed in anamount ranging from 0.02 to 0.15% by weight based on the weight of milktogether with other additives such as sugar, etc.

Separation or flotation of fats is not caused in the milk fermented bylactic acid in which the fatty acid esters composition of apolyglycerine is mixed even at low temperatures such as 5° C. or hightemperatures such as 30° C. for a long time of period such as 3 months.

For meat or fish meat, the fatty acid esters composition of apolyglycerine is employed in an amount ranging from 0.1 to 5% by weight,preferably from 0.5 to 1% based on the weight of meat or fish meatincluding moisture together with other additives such as salt and eggwhite, etc.

In the case when the fatty acid esters composition of a polyglycerine ofthe present invention is employed in the meat or fish meat, it acts as aelasticity improver and a whiteness improver.

The fatty acid esters composition of a polyglycerine of the presentinvention can be employed together with a oils&fats composition such assoy bean oil, etc. as an emulsifier for bread-stuffs, cake, and cookies,etc. as described in JP-A-22690/1994, together with an oils & fatscomposition for butter cake as described in JP-A-53/1994, together withwater, sorbitol, lactose, and whey protein, etc. for sponge cake orsnack cake as described in JP-A-269244/1994, as an O/W type-emulsifiedoil&fat composition which contains water, oils & fats, a glucide such assorbitol, and an emulsifier as described in JP-A-78672/1994, togetherwith a fatty acid ester of sugar, a fatty acid ester of glycerine, afatty acid ester. of sorbitan, a crystallized cellulose, etc. as astabilizer for emulsifying as described in JP-A-125711/1994, togetherwith cacao components, milk components, a sweetening agent, and water asan emulsifier for a cacao drink as described in JP-A-38682/1994,together with egg, starch, and vegetable oils, etc. as an emulsifier fornoodles as described in JP-A-276972/1994 and JP-A-197717/1994, as animprover for fish meal as described in JP-A-22730/1994, as an improverfor scallop meal as described in JP-A-90713/1994, as a plasticizer forgranules containing proteins as described in JP-A-133735/1994, as anemulsifier for a W/O type oil & fat composition as described inJP-A-209704/1994, as a stabilizer for a wheat powder composition asdescribed in JP-A-253718/1994, as an emulsifier for an oils & fatscomposition as described in JP-A-14711/1994, as an emulsifier for afermented milk or cheese as described in JP-A-113799/1994, as astabilizer for an extract from plants as described in JP-A-153884/1994,as a stabilizer for starch-based food-stuffs as described inJP-A-225684/1994, as a stabilizer for an oils & fats-containingfermented drink as described in JP-A-62734/1994, as a stabilizer for awater-containing chocolate base as described in JP-A-189682/1994, as astabilizer for an oils & fats composition as described inJP-A-90663/1994, and as an emulsifier for food-stuffs containingproteins as described in JP-A-113727/1994, etc.

According to a sixth aspect of the present invention, there is provideda resin composition which comprises a fatty acid esters composition of apolyglycerine in the first aspect or a highly-purified fatty acid esterscomposition of a polyglycerine in the fourth aspect, and a thermoplasticresin.

As examples of the thermoplastic resin to be applied, there arespecifically exemplified a polyvinyl chloride resin, a styrene-basedresin, a methylmethacrylate-based resin, and a polyacetal resin, etc.

The fatty acid esters composition of a polyglycerine of the first aspectand a highly-purified fatty acid esters composition of a polyglycerineof the fourth aspect in the present invention act as a plasticizer, animprover of a wetting ability for a hydrophobic resin, an improver of aprinting property, an anti-static agent, a releasing agent, or ananti-clouding agent, etc. for a variety of thermoplastic resins.

As an additive for a variety of thermoplastic resins, the fatty acidesters composition of a polyglycerine in the first and fourth aspectsare employed in an amount ranging from 0.01% to 10% by weight,preferably from 0.05 to 5% by weight, and more preferably from 0.1 to 3%by weight based on the amount of the resins, although it depends uponthe kind of the thermoplastic resins.

Mixing or kneading of the fatty acid esters composition of apolyglycerine with the thermoplastic resins can be carried out withoutany limitations by a single or twin screw extruder, a kneader, a rollmixer, a tumble mixer, a Brabender type mixer, a Henshell mixer, and aBanbury mixer which have been conventionally employed.

Furthermore, monomers can also be polymerized in the presence of thefatty acid esters composition of a polyglycerine depending upon the kindof thermoplastic resins.

In the case when the fatty acid esters composition of a polyglycerine isemployed as an additive for a variety of thermoplastic resins, it can beemployed solely or in combination.

Still further, in the case when the fatty acid esters composition of apolyglycerine is employed as an additive for thermoplastic resins, itcan be employed together with other conventional additives such as ananti-oxidant which includes a hindered phenol-based or sulphur-basedcompound, a stabilizer, a flame retardant, a slipping agent, anucleating agent, an ultraviolet absorbent, a releasing agent, acoloring agent, pigments, fibers, and fillers such as fiber glass orglass beads, etc., depending upon uses.

A resin composition in which a resin is mixed with the fatty acid esterscomposition of a polyglycerine of the first aspect or the fourth aspectin the present invention and other additives can be molded by extrudingmolding, injection molding, compression molding, vacuum molding, blowmolding, and foamed molding, etc.

For example, in the case when the fatty acid esters composition of apolyglycerine of the first aspect or fourth aspect is employed as anadditive for a polyvinyl chloride resin for the purpose of preparing aresin composition, particularly, it effectively acts as an anti-staticagent.

A polyvinyl chloride resin may be molded as a film or a molded articlewhich includes a plasticized or rigid polyvinyl chloride resin.

The fatty acid esters composition of a polyglycerine of the first aspector fourth aspect is employed in an amount ranging from 1 to 10 parts byweight, and preferably from 2 to 7 parts by weight based on 100 parts ofthe polyvinyl chloride resin.

In the case when the amount is below 1 part by weight, an anti-staticeffect is poor and, on the contrary, in the case when the amount exceeds10 part by weight, not only transparency of films decreases but alsoworkability in molding process of the films unpreferably decreases.

The fatty acid esters composition of a polyglycerine of the first aspector the highly purified fatty acid esters composition of a polyglycerineof the fourth aspect may be employed solely or in combination, andfurther may be employed together with conventional anti-static agentssuch as fatty acid esters of a glycerine, fatty acid esters of sorbitan,and sodium alkylsulfonates, etc.

The polyvinyl chloride resin to be employed in the present inventionincludes homopolymers and copolymers with olefines such as ethylene orpropylene, vinyl acetate, and vinylidene chloride.

Furthermore, the fatty acid esters composition of a polyglycerine may beoptionally employed together with conventional additives such as thermalstabilizers, anti-oxidants, reinforcing materials, processing agents,ultraviolet absorbents, slipping agents, coloring materials such asdyes, and pigments, etc.

In the meantime, for example, in the case when the fatty acid esterscomposition of a polyglycerine of the first aspect or the highlypurified fatty acid esters composition of a polyglycerine of the fourthaspect is employed as an additive for a styrene-based resin for thepurpose of preparing a resin composition, particularly, it effectivelyacts as an anti-clouding agent or an anti-static agent.

As specific examples of the styrene-based resin, there are exemplified astyrene homopolymer, a high impact polystyrene, an acrylonitrile-styrenecopolymer, a styrene-methylmethacrylate copolymer, and astyrene-methylmethacrylate-acrylonitrile copolymer.

In particular, in the case when it is employed as an additive for astyrene-based resin film for the purpose of wrapping food-stuffs, it isexceedingly effective.

The fatty acid esters composition of a polyglycerine of the first aspector the highly purified fatty acid esters composition of a polyglycerineof the fourth aspect is employed in an amount ranging from 0.5 to 8.0%by weight, and preferably from 1 to 5% by weight based on the weight ofthe styrene-based resin.

In the case when the amount is below 0.8% by weight, an anti-cloudingeffect is poor and, on the contrary, in the case when the amount exceeds8% by weight, the anti-clouding agent excessively bleeds out of thefilms, resulting in that film surfaces are unpreferably sticky.

In the case when the fatty acid esters composition of a polyglycerine ofthe first aspect or the highly purified fatty acid esters composition ofa polyglycerine of the fourth aspect is employed as an additive for astyrene-methylmethacrylate-acrylonitrile resin which is one of thestyrene-based resin, particularly, it effectively acts as an anti-staticagent.

The styrene-based resin includes styrene units ranging from 100% to 20%by weight, and there may be included methyl methacrylate units rangingfrom 0% to 80% by weight and acrylonitrile units ranging from 0% to 20%by weight as other units.

Furthermore, the styrene-based resin can be mixed with the fatty acidesters composition of a polyglycerine of the first aspect or the highlypurified fatty acid esters composition of a polyglycerine of the fourthaspect in combination with phosphorus compounds and further optionally apolyalkylene glycol for the purpose of preparing a transparent resincomposition having an excellent anti-static property.

As examples of the phosphorus compounds to be employed in the presentinvention, there are exemplified tributyl phosphite, triisooctylphosphite, tribenzyl phosphite, triphenyl phosphite, phenyldidecylphosphite, diphenylisodecyl phosphite, trisnonyl phenyl phosphite,tridecyl phosphite, trisstearyl phosphite, distearylpentaerythritoldiphosphite, and the like.

Of those, there are preferably employed tridecyl phosphite, trisstearylphosphite, and distearylpentaerythritol diphosphite.

The fatty acid esters composition of a polyglycerine of the first aspector the highly purified fatty acid esters composition of a polyglycerineof the fourth aspect is employed in an amount ranging from 0.5 to 6.0parts by weight, and preferably from 1.0 to 5.0 parts by weight based on100 parts by weight of the transparent resin composition.

In the case when the amount is below 0.6 part by weight, an anti-staticeffect is poor and, on the contrary, in the case when the amount exceeds6.0 parts by weight, the esters composition unpreferably bleeds out ofarticles, and further the surface of a mold becomes unpreferably dirty.

The phosphorus compounds are employed in an amount ranging from 0.05 to4.0 parts by weight, and preferably from 1.0 to 3.0 parts by weightbased on 100 parts by weight of the transparent resin composition.

In the case when the amount is below 0.05 part by weight, an anti-staticeffect is unpreferably poor and, on the contrary, in the case when theamount exceeds 4.0 parts by weight, the phosphite compounds adhere tosurface of a mold or a molded article, unpreferably resulting in that amolded article becomes dirty.

The polyalkylene glycol which is an optional component is employed in anamount ranging from 0.5 to 5.0 parts by weight, and preferably from 1.0to 4.0 parts by weight based on 100 parts by weight of the transparentresin composition.

In the case when the amount is below 0.5 part by weight, an effect foraccelerating the anti-static is unpreferably poor and, on the contrary,in the case when the amount exceeds 5.0 parts by weight, thepolyalkyleneglycol oozes out of an molded article, unpreferablyresulting in that a molded article becomes dirty.

The polyalkylene glycol has a molecular weight ranging from 200 to 1500,and preferably from 300 to 1000. In the case when the molecular weightis below 200, compatibility with the resin becomes unpreferably poorand, on the contrary, in the case when the molecular weight exceeds1500, an effect for accelerating the anti-static becomes unpreferablypoor.

The styrene-based resin, the fatty acid esters composition of apolyglycerine, the phosphorus compounds, and optionally the polyalkyleneglycol can be mixed with the conventional mixers described hereinabove.

In the meantime, for example, in the case when the fatty acid esterscomposition of a polyglycerine of the first aspect or the highlypurified fatty acid esters composition of a polyglycerine of the fourthaspect is employed as an additive for a methyl-methacrylate-based resinfor the purpose of preparing a resin composition, particularly, iteffectively acts a releasing agent in a molding process.

Methylmethacrylate-based resin in the present invention includes amethylmethacrylate homopolymer and a copolymer with acrylates such asmethylacrylate, ethylacrylate, butylacrylate, methacrylates such asethylmethacrylate, butylmethacrylate, cyclohexylmethacrylate, acrylicacid, methacrylic acid, styrene, acrylonitrile, diene-based monomers,glutaric acid anhydride, and gulutarimide, etc.

In the case when the fatty acid esters composition of a polyglycerine ofthe first aspect or the highly purified fatty acid esters composition ofa polyglycerine of the fourth aspect is employed as a releasing agentfor a methylmethacrylate-based resin, it is preferably employed togetherwith pentaerythritols or fatty acid esters thereof in order toaccelerate a releasing effect.

The pentaerythritols include monopentaerythritol, dipentaerythritol,tripentaerythritol, tetrapentaerythritol, and adducts of 1 to 5 mol ofethyleneoxide or propyleneoxide with the pentaerythritols.

Furthermore, the fatty acid esters thereof include esters of thepentaerythritols with fatty acids such as caproic acid, caprylic acid,2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid,myristic acid, palmitic acid, palmitoreic acid, stearic acid, isostearicacid, oleic acid, linoleic acid, behenic acid, erucic acid, licinoleicacid, and hydroxystearic acid, etc.

The pentaerythritols or the fatty acid esters thereof are employed in aratio ranging from 10/90 to 90/10, and preferably from 25/75 to 75/25based on the weight of the fatty acid esters composition of apolyglycerine.

The fatty acid esters composition of a polyglycerine of the first aspector fourth aspect or a mixture with the pentaerythritols or the fattyacid esters thereof is employed in an amount ranging from 0.01 to 0.5%by weight, and preferably from 0.1 to 0.2% by weight based on the weightof the methyl-methacrylate-based resin.

In the case when the amount is below 0.01% by weight, a releasing effectis insufficient and, on the contrary, in the case when the amountexceeds 0.5% by weight, not only transparency of the resin isunpreferably adversely affected, but also the releasing agents move tothe surface of molded articles, unpreferably resulting in that thesurface of the mold or molded articles becomes dirty by excessiveamounts of the releasing agent, and commercial values remarkablydecrease by coloration of the molded article.

Furthermore, there may be optionally mixed conventional additives suchas hindered amine-based light stabilizers, hindered phenol-based,phosphorus-based, and sulphur-based anti-oxidants, reinforcing materialssuch as glass fibers, processing agents, ultraviolet absorbents,slipping agents, flame-retardants, weatherable agent, coloring agentssuch as dyes, and thermal stabilizers, etc.

In the meantime, for example, in the case when the fatty acid esterscomposition of a polyglycerine of the first aspect or the highlypurified fatty acid esters composition of a polyglycerine of the fourthaspect can be employed as an additive for a polyacetal resin for thepurpose of preparing a resin composition, particularly, it effectivelyacts as an agent for improving a printing property, an agent forimproving wetting property to water, water-based inks, and an aqueousserum, and an agent for improving releasing property from a molding die.

Furthermore, the excellent properties endure for a long time of period.

In the case when the fatty acid esters composition of a polyglycerine ofthe first aspect or the highly purified fatty acid esters composition ofa polyglycerine of the fourth aspect is employed as an agent forimproving a printing property, it is employed in an amount ranging from0.01 to 5 parts by weight, and preferably from 0.03 to 1 parts byweight, and more preferably from 0.05 to 0.08 part by weight based on100 parts of the polyacetal resin.

In the case when the amount is below 0.01 part by weight, an effect forimproving printing property is small and, on the contrary, in the casewhen the amount exceeds 5 parts by weight, thermal stabilityunpreferably decreases, and silver streak is caused by decomposed gaseswhen molded, unpreferably resulting in that outer appearances of moldedarticles become remarkably poor.

In the case when the fatty acid esters composition of a polyglycerine ofthe first aspect or the highly purified fatty acid esters composition ofa polyglycerine of the fourth aspect is employed as an additive forimproving a wetting property, it is employed in an amount ranging from0.01 to 0.4% by weight, and preferably from 0.05 to 0.3% by weight, andmore preferably from based on the weight of the polyacetal resin.

In the case when the amount is below 0.01% by weight, an effect forimproving wetting property is small and, on the contrary, in the casewhen the amount exceeds 0.4% by weight, mechanical property unpreferablydecreases, and melt viscosity occasionally decreases, unpreferablyresulting in that molding conditions are remarkably limited for thepurpose of manufacturing a delicate part such as an ink jet nozzle in aprinter for a personal computer.

In the case when the fatty acid esters composition of a polyglycerine ofthe first aspect or fourth aspect is mixed with the polyacetal resin inan amount ranging from 0.01 to 0.4% by weight, a resin composition hasMelt Index (based on ASTM D1238-89) of below 1.5, an article molded fromthe resin composition has a contact angle of below 50, resulting inbeing preferred for the purpose of manufacturing a delicate part such asan ink jet nozzle in a printer for a personal computer.

The polyacetal resin to be employed in the present invention includes ahigh molecular weight compound having oxymethylene groups —CH₂O—. Morespecifically, there are included an oxymethylene homopolymer (—CH₂O—)n—which is prepared by polymerization of formaldehyde or a cyclic oligomersuch as trimer (trioxane) of formaldehyde and tetramer (tetraoxane) offormaldehyde. Furthermore, there is included an oxymethylene copolymerhaving a structure, for example, such as (—CH₂O—)n—(—CH₂—CH₂O—)m— having0.1 to 20% by weight of oxyalkylene units containing a carbon numberranging from 2 to 8.

The copolymer is prepared by a reaction of formaldehyde or a cyclicoligomer such as trimer (trioxane) of formaldehyde and tetramer(tetraoxane) of formaldehyde with a cyclic ether such as ethylene oxide,propylene oxide, epichlorohydrin, 1,3-dioxolan, a formal of a glycol,and a formal of a diglycol, etc.

Still further, there is included an oxymethylene block copolymer havingmore than 50% by weight of recurring units a branched oxymethylenecopolymer or oxymethylene and less than 50% by weight of other polymerunits.

In addition, there can be blended at least one of an oxymethylenehomopolymer, an oxymethylene copolymer, a branched polymer, and anoxymethylene block copolymer.

There is preferably employed a polyacetal resin having an FR value (ASTMD1238-57E) of 20-100 g/10 minutes in the present invention. In the casewhen the FR value is below 20 or exceeds 100, printing property cannotbe improved.

In the polyacetal resin, there can be preferably mixed a hindered aminecompound together with the fatty acid esters composition of apolyglycerine.

Hindered amine compound specifically includes4-acetoxy-2,2,6,6-tetramethylpiperidine,4-stearoiloxy-2,2,6,6-tetramethylpiperidine,4-acryloiloxy-2,2,6,6-tetramethyl piperidine,4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine,4-benzoiloxy-2,2,6,6-tetramethylpiperidine,4-methoxy-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethyl piperidine,4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine,4-benzyloxy-2,2,6,6-tetramethylpiperidine,4-phenoxy-2,2,6,6-tetramethylpiperidine,4-ethylcarbamoyloxy-2,2,6,6-tetramethyl piperidine,4-phenylcarbamoyloxy-2,2,6,6-tetramethylpiperidine,bis(2,2,6,6-tetramethyl-4-piperidyl)-carbonate,bis(2,2,6,6-tetramethyl-4-piperidyl)-oxalate,bis(2,2,6,6-tetramethyl-4-piperidyl)-malonate,bis(2,2,6,6-tetramethyl-4-piperidyl)-adipate,bis(2,2,6,6-tetramethyl-4-piperidyl)-terephthalate,bis(2,2,6,6-tetramethyl-4-piperidyl)-ethane,′-bis(2,2,6,6-tetramethyl-4-piperidyl)-p-xylene,bis(2,2,6,6-tetramethyl-4-piperidyl)-tollylene-2,4-dicarbamate,bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate,tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,5-tricarboxylate, andtris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate, etc.

Furthermore, in the polyacetal resin, there can be preferably mixed anadditive such as beta-alanine polymer, a polyamide such as 6,6-nylon,6,10-nylon, thermal stabilizers such as melamine, anti-oxidants such as2,2′-methylenebis(4-methyl-6-t-butylphenol),triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],slipping agents, reinforcing materials such as glass fibers, carbonfibers, inorganic fillers such as potassium titanate fibers, fibroustitanium oxides, glass beads, talc, calcium carbonate, releasing agents,plasticizers, carbon black, and pigments, etc., together with the fattyacid esters composition of a polyglycerine.

In order to promote a printing ability of a resin composition in whichthe polyacetal resin are mixed with the fatty acid esters composition ofa polyglycerine of the first aspect or the highly purified fatty acidesters composition of a polyglycerine of the fourth aspect, a hinderedamine compound, and other additives, the thickness of skin layer in amolded article is preferably controlled within 15 microns.

The skin layer in the molded article means an outer surface layer atside portion in a sliced sample through which light is not polarizedwhen observed by a light-transmittable type polarizing microscope of340-magnifications using a cross nicol.

The sliced sample is prepared by slicing cross section of a moldedarticle in the thickness of 10 microns with a microtome.

The thickness of the skin layer can be adjusted by controllingcrystallization time of resin or selecting an appropriate moldingmethod, or the combination thereof.

As the method for controlling crystallization time of resin, there is amethod in which crystallization time of molded articles is controlled ina range of 20 to 100 seconds.

Crystallization time in the present invention means a time of period(second) until an exothermal peak accompanied by crystallization ofpolyacetal resin is detected after temperature of a sample holderattained to 150° C. as described below.

The temperature of 5 mg of the polyacetal resin is heated to 200° C. atthe rate of 320° C./minute, and maintained at 200° C. for 2 minutes,followed by cooling until 150° C. at the rate of 80° C./minute.

As the method for controlling crystallization time in a range of 20 to100 seconds, there is a method in which there are mixed an appropriateamount of a nucleating agent such as talc, silicate powder,hydrotalcite, calcium carbide, amine-based compound such as melamine ordicyandiamide, nitrides such as boron nitride, zinc oxide, titaniumoxide, calcium oxide, magnesium oxide, carbon black such as conductingcarbon black, and an organic nucleating agent such as a branchedpolyacetal copolymer, polyamides such as 6,6-nylon, an ionic polymer ofacrylamide, and powder of vinyl polymers, etc.

Of those, there are preferably employed nitrides such as boron nitride,and polyamides such as 6,6-nylon or an ionic polymer of acrylamide, andmost preferably boron nitride.

There is preferably employed a boron nitride having an averaged particlesize of from 1 to 10 microns, preferably from 2 to 7 microns.

Subsequently, there is described a method for controlling the thicknessof the skin layer by selecting an appropriate molding method.

The process includes (1) a method in which molding is carried out atmold temperatures ranging from 100 to 150° C., preferably from 110 to140° C., (2) a method in which injection molding is carried out byselectively heating cavities in a mold for injection molding with aninduction heating method by microwave, (3) a method in which an articleis compressively molded with a thermal roll, and then gradually cooled,and (4) a method in which an article is molded at the mold temperatureranging from 10 to 100° C., and then molded article is thermallyannealed at the temperature ranging from 150° C. to a melting point of apolyacetal resin.

Of those, the methods (1) and (2) are preferably employed from viewpointof productivity.

Polyacetal resin composition in which a polyacetal resin is mixed withthe fatty acid esters composition of a polyglycerine of the first aspector the highly purified fatty acid esters composition of a polyglycerineof the fourth aspect in the present invention and other additives ispreferably used as a lever, an instrumental panel, a dial plate for ataping writer, a knob for a combination switch, housings, and a shutterfor a disk or a magnetic tape cartridge. More preferably, it is employedas a shutter for a disk or a magnetic tape cartridge.

Furthermore, polyacetal resin composition in which a polyacetal resin ismixed with the fatty acid esters composition of a polyglycerine of thefirst aspect or the highly purified fatty acid esters composition of apolyglycerine of the fourth aspect in the present invention in order toimprove wetting property is preferably employed as an ink jet nozzle ina printer for a personal computer.

In order to prepare another polyacetal resin composition, in the casewhen the fatty acid esters composition of a polyglycerine of the firstaspect or the highly purified fatty acid esters composition of apolyglycerine of the fourth aspect is mixed together with a hinderedphenol-based compound, fibrous titanium oxide, and at least one selectedfrom the group consisting of a compound having nitrogen, a hydroxide ofalkaline metal or alkaline earth metal, a metal salt of a carboxylicacid or an inorganic acid, and a polyacetal resin, it acts as areleasing agent from a molding die or an agent for improving fluidity ina molding die.

The above-described polyacetal resin composition is preferably employedas small or precise parts having thin thickness for precisioninstruments such as a watch, a printer, and a desk-top electroniccalculator, etc., because of being excellent in mechanical propertiesand dimensional stability.

In the above-described polyacetal resin composition for precisioninstruments, although the polyacetal resin is not limited regardless ofhomopolymers or copolymers described hereinabove and polymerizationdegree thereof, there is preferably employed a polyacetal resin havingan FR value (ASTM D1238-57E) of more than 7 g/10 minutes.

The surface of the fibrous titanium oxide is preferably processed.Unprocessed fibrous titanium oxide causes decomposition and foaming inthe resin composition during compounding and/or molding.

The fibrous titanium oxide has preferably an aspect ratio of more than10. In the case when the ratio is below 10, an reinforcing effect is notshown.

Average diameter of the fibrous titanium oxide preferably ranges from0.02 to 0.6 microns, and average length of the fibrous titanium oxidepreferably ranges from 1 to 20 microns.

The fibrous titanium oxide is preferably employed in an amount rangingfrom 1 to 70 parts by weight, preferably from 10 to 50, more preferablyfrom 20 to 40 based on 100 parts by weight of the acetal resin.

In the case when the ratio is below 1, an reinforcing effect is notshown, and in the case when the ratio exceeds 70, fluidity is not onlyremarkably lowers but also thermal stability of the resin compositionunpreferably decreases.

As agents for processing the surface of the fibrous titanium oxide,there can be limitlessly employed silan-based coupling agents,titanate-based coupling agents, aluminum-based coupling agents, andzirconate-based coupling agents which have been conventionally employed.

Specifically, there are exemplified N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane,isopropyltristearoyltitanate, diisopropoxyaluminumethylacetate, andn-butylzirconate, etc.

Furthermore, granulated fibrous titanium oxides are particularlypreferably employed because of more excellent workability in a mixingprocess compared to no-granulated fibrous titanium oxides. However,fibrous titanium oxides which are too strongly granulated are notpreferred because of not being sufficiently loosened, unpreferablyresulting in insufficient dispersion of the fibrous titanium oxides anddecrease of mechanical properties in a molded article.

As the compound having nitrogen, there are specifically exemplifiedpolyamide polymers or copolymers such as nylon 12, nylon 610, nylon 6,and nylon 66, polyamides having substituent groups such as methylolgroup, nylon salts, polyamides such as polyester amides which areprepared from caprolactones and caprolactams, polyaminotriasol,dihydrazide dicarboxylate such as hydrazide oxalate, hydrazide adipate,and hydrazide sebacate, a condensate thermally prepared from urea, acondensed polymer having nitrogen prepared from urea and diamines,uracyls, cyanoguanidines, dicyandiamide,guanamine(2,4-diamino-sym-triadine),melamine(2,4,6-triamino-sym-triadine), N-butylmelamine,N-phenylmelamine, N,N-diphenylmelamine, N,N-diallylmelamine,N,N′,N″-triallylmelamine, N,N′,N″-trimethylolmelamine,benzoguanamine(2,4-diamino-6-phenyl-sym-triadine),2,4-diamino-6-methyl-sym-triadine, 2,4-diamino-6-butyl-sym-triadine,2,4-diamino-6-benzyloxy-sym-triadine, 2,4-diamino-6-butoxy-sym-triadine,2,4-diamino-6-cyclohexyl-sym-triadine,2,4-diamino-6-chloro-sym-triadine, 2,4-diamino-6-mercapto-sym-triadine,2,4-dioxy-6-amino-sym-triadine, 2-oxy-4,6-diamino-sym-triadine,2,4-diamino-6-methyl-sym-triadine,N,N′,N′,N′-tetracyanoethylbenzguanamine, and a melamine-formaldehydecondensate, etc.

Of those, there are preferably employed a melamine, a melaminederivative, and a melamine-formaldehyde condensate, etc.

As the hydroxide of alkaline metal or alkaline earth metal, the metalsalt of a carboxylic acid or an inorganic acid, there are specificallyexemplified alkali metallic salts such as lithium salts, sodium salts,and potassium salts, alkali earth metallic salts such as magnesiumsalts, calcium salts, and barium salts, inorganic acid salts such ascarbonates, phosphates, and silicates. As the carboxylic acids, thereare specifically exemplified oxalic acid, malonic acid, succinic acid,and higher fatty acids having a carbon number ranging from 12 to 32 suchas stearic acid and behenic acid, and higher fatty acids havingsubstituted group such as hydroxyl group.

Of those, there are preferably employed the hydroxide of lithium,magnesium, and calcium, carbonates, and more preferably carboxylates.

As particularly preferred carboxylates containing metals, there areexemplified calcium stearate, calcium 12-hydroxy-stearate, and calciumbehenate.

The compound having nitrogen, the hydroxide of alkaline metal oralkaline earth metal, and the metal salt of carboxylic acid or inorganicacid may be employed solely or in combination.

Those are employed in an amount ranging from 0.01 to 5 parts by weight,preferably from 0.03 to 2 parts by weight, and more preferably from 0.05to 1 part by weight based on 100 parts by weight of the polyacetalresin.

In the case when the amount is below 0.01 part by weight, a releasingeffect from a molding die, an effect for improving fluidity in themolding die, and thermal stability of molded articles becomeinsufficient and, on the contrary, in the case when the amount exceeds 5parts by weight, those move to the surface of molded articles,unpreferably resulting in that the surface of the molding die or moldedarticles become dirty by excessive amounts of those, and commercialvalues remarkably decrease by coloration of the molded article.

Furthermore, hindered phenol-based compounds can be mixed together withthe above-described compound having nitrogen, hydroxide of alkalinemetal or alkaline earth metal, and metal salt of carboxylic acid orinorganic acid in order to control thermal decomposition of polyacetalresins.

As the hindered phenol-based compounds, there are specificallyexemplified 2,2-methylenebis(4-methyl-6-butyl phenol),1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate],pentaerythrityltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxy-benzyl)benzene,n-octadecyl-3-(4′-hydroxy-3′,5,-di-t-butylphenol)propionate,4,4′-butylidene-bis-(6-t-butyl-3-methyl-phenol),distearyl-3,5-di-t-butyl-4-hydroxybenzyl phosphonate,2-t-butyl-6-(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenylacrylate,and N,N′-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydroynamide).

Those may be employed solely or in combination.

Of those, there are particularly preferred 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],pentaerythrityltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate],triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],N,N′-hexamethlylenebis(3,5-di-t-butyl-4-hydroxy-hydroynamide).

The hindered phenol-based compounds are employed in an amount rangingfrom 0.01 to 5 parts by weight, and preferably from 0.1 to 3 parts byweight based on 100 parts by weight of the polyacetal resin.

In the case when the amount is below 0.01 part by weight, thermalstability of molded articles become insufficient and, on the contrary,in the case when the amount exceeds 5 parts by weight, those move to thesurface of molded articles, unpreferably resulting in that the moldedarticles become dirty by excessive amounts of those.

In the case when the fatty acid esters composition of a polyglycerine ofthe first aspect or fourth aspect is employed as an agent for improvinga releasing property from a molding die or an agent for improvingfluidity in the molding die, it is employed in an amount ranging from0.01 to 5 parts by weight, and preferably from 0.1 to 2 parts by weightbased on 100 parts by weight of the polyacetal resins.

In the case when the amount is below 0.01 part by weight, an effect forimproving the releasing property or fluidity is small and, on thecontrary, in the case when the amount exceeds 5 parts by weight,bleeding in the surface of the molded articles is unpreferably caused.

The above-described polyacetal resin composition is preferably employedas small or precise parts having thin thickness for precisioninstruments such as a watch, a printer, and a desk top electroniccalculator, etc., because of being excellent in mechanical properties,thermal stability and dimensional stability.

In the meantime, the fatty acid esters compositions of a polyglycerineof the first aspect or fourth aspect in the present invention are alsouseful as an additive for cosmetics, toiletries, and detergents.

According to a seventh aspect of the present invention, there isprovided a water-in-oil type-emulsified composition for cosmetics whichcomprises glycerine, oils and/or waxes, water, and a fatty acid esterscomposition of a polyglycerine in the first aspect or a highly-purifiedfatty acid esters composition of a polyglycerine in the fourth aspect.

In the water-in-oil type-emulsified composition for cosmetics, the fattyacid esters composition of a polyglycerine or the highly-purified fattyacid esters composition of a polyglycerine is employed in an amountranging from 1.0 to 10.0% by weight, preferably from 2.0 to 5.0%, andmore preferably from 3 to 4% by weight based on the total weight of thewater-in-oil type-emulsified composition for cosmetics of the presentinvention.

In the case when it is below 1.0% by weight, stability for long time ofperiod becomes worse and, on the contrary, in the case when it exceeds10.0% by weight, viscosity becomes high or stability for long time ofperiod becomes worse.

In the water-in-oil type-emulsified composition for cosmetics, there ismore preferably employed the highly-purified fatty acid esterscomposition of a polyglycerine in the fourth aspect from viewpoint ofthe use for human body.

In the water-in-oil type-emulsified composition for cosmetics, glycerineis an essential component. Glycerine is employed in an amount rangingfrom 5 to 25% by weight, preferably from 10 to 20%, and more preferablyapproximately 15% by weight based on the total weight of thewater-in-oil type-emulsified composition for cosmetics of the presentinvention.

In the case when it is below 5% by weight, stability for long time ofperiod becomes worse and, on the contrary, in the case when it exceeds25% by weight, a feel in use becomes worse because of strong stickiness.

In the water-in-oil type-emulsified composition for cosmetics, oilsand/or waxes include hydrocarbons such as a liquid paraffin, a solidparaffin, vaseline, and a microcrystalline wax, esters such as isopropylmyristate, cetyl 2-ethylhexanate, cetyl palmitate, myristyl myristate,propyleneglycol dicaprylate, and tri(caprylic acid and capricacid)glyceryl, animal or vegetable oils/waxes such as bees-waxes,whale-waxes, lanolin, olive oils, etc. Of those, liquid paraffin andvaseline are employed in a relatively larger amount.

The oils and/or waxes are employed in an amount ranging from 10 to 40%by weight, preferably from 15 to 30%, and more preferably 20 to 25% byweight based on the total weight of the water-in-oil type-emulsifiedcomposition for cosmetics of the present invention.

In the case when it is below 10% by weight, viscosity becomes too high,resulting in that it is not thinly extended and, on the contrary, in thecase when it exceeds 40% by weight, an oily feel becomes too strong andstability for a long time of period becomes deteriorated.

Water is employed in an amount ranging from 25 to 50% by weight,preferably from 30 to 40%, and more preferably 30 to 35% by weight basedon the total weight of the water-in-oil type-emulsified composition forcosmetics of the present invention.

In the case when it is below 25% by weight or in the case when itexceeds 50% by weight, a good feel in use and stability for a long timeof period become unpreferably deteriorated.

Furthermore, the water-in-oil type-emulsified composition for cosmeticsof the present invention can optionally include other surface activeagents, water-soluble solvents such as propyleneglycol and ethanol,organic or inorganic fillers such as finely-sized titanium oxide,powdered nylon, talc, kaolin, ultraviolet absorbents, antiseptics,anti-oxidants, water soluble salts such as magnesium sulphate, medicinalcomponents, coloring agent, and perfumes, etc. which are conventionallyemployed as additives for cosmetics.

The water-in-oil type-emulsified composition for cosmetics of thepresent invention can be used for cleansings, face massage, and ananti-sunburn agent for human body, etc.

According to an eighth aspect of the present invention, there isprovided a transparent liquid composition for cosmetics which comprisesat least one of an non-ionic surface active agent, at least one ofwater-soluble compound having at least two hydroxyl groups, oilycomponents, water, and a fatty acid esters composition of apolyglycerine in the first aspect or a highly-purified fatty acid esterscomposition of a polyglycerine in the fourth aspect.

In the eighth aspect of the present invention, there is more preferablyemployed a highly-purified fatty acid esters composition of apolyglycerine in the fourth aspect from viewpoint of the use for humanbody.

As the non-ionic surface active agent, there are specifically employed afatty acid esters composition of sorbitan, a fatty acid esterscomposition of glycerine, a fatty acid esters composition ofpolyethyleneglycol, a polyoxyethylene alkylether, a polyoxyethylenealkylphenylether, a hydrogenated castor oil of polyoxyethylene, a fattyacid esters composition of polyoxyethylene sorbitan, and a fatty acidesters composition of polyoxyethylene sorbitol, etc.

In the transparent liquid composition for cosmetics of the presentinvention, the fatty acid esters composition of a polyglycerine or thehighly-purified fatty acid esters composition of a polyglycerine isemployed in combination with at least one of the non-ionic surfaceactive agent in an amount ranging from 5 to 40% by weight, preferablyfrom 15 to 30%, and more preferably 15 to 20% by weight based on thetotal weight of the transparent liquid composition for cosmetics.

In the case when it is below 5% by weight or in the case when it exceeds40% by weight, the liquid composition unpreferably decreasestransparency, or it unpreferably gels.

HLB value ranges from 8 to 13, and preferably from 9 to 11 in a mixturecomposed of the fatty acid esters composition of a polyglycerine or thehighly-purified fatty acid esters composition of a polyglycerine and atleast one of the non-ionic surface active agent. In the case when it isbelow 8, or in the case when it exceeds 13, the liquid compositionunpreferably decreases transparency, or it unpreferably emulsifies orgels.

In the transparent liquid composition for cosmetics of the presentinvention, as the water-soluble compound having at least two hydroxylgroups, there are specifically employed propylene glycol,1,3-butanediol, dipropylene glycol, glycerine, diglycerine,polyglycerine, trimethylolpropane, erythritol, pentaerythritol,isopreneglycol, sorbitan, glucose, sorbitol, maltitol, saccharose,polyoxyethylene methylglucoside, diethyleneglycol, andpolyethyleneglycol. Of those, there are preferably employed1,3-butanediol, propylene glycol, and dipropylene glycol.

At least one of tie water-soluble compound having at least two hydroxylgroups is employed in an amount ranging from 2 to 40% by weight,preferably from 4 to 25% by weight based on the total weight of thetransparent liquid composition. In the case when it is below 2%, or inthe case when it exceeds 25%, the liquid composition unpreferablydecreases transparency, or it unpreferably emulsifies or gels.

In the transparent liquid composition for cosmetics of the presentinvention, the oily components include vegetable oils, mineral oils, andester oils.

More specifically, there are employed beef tallow, squalane, olive oil,peanut oil, sweet almond oil, castor oil, corn oil, a liquid paraffin,vaseline, tri(caprylic acid and capric acid)glyceryl, isopropylmyristate, vitamin E acetate, pyridoxine dioctanoate, myristylmyristate, octyldodecanol oleate, lanolin, fatty acid derivatives oflanolin, methylpolysiloxane, and an isostearyl cholesterylester, etc.

Those may be employed solely or in combination.

The oily components are employed in an amount ranging from 3 to 70% byweight, preferably from 10 to 60%, and more preferably 15 to 30% byweight based on the total weight of the transparent liquid compositionfor cosmetics.

In the transparent liquid composition for cosmetics of the presentinvention, water is employed in an amount ranging from 0.5 to 80% byweight, and preferably from 2 to 60% by weight based on the total weightof the transparent liquid composition for cosmetics. In the case when itis below 0.5%, or in the case when it exceeds 80%, the liquidcomposition occasionally decreases transparency.

The transparent liquid composition for cosmetics of the presentinvention can be prepared by conventional mixing methods.

As a preferred preparation method, there is exemplified a method inwhich there are firstly mixed the fatty acid esters composition of apolyglycerine or the highly-purified fatty acid esters composition of apolyglycerine and at least one of the non-ionic surface active agent,and then the oily components are mixed, followed by gradually mixingwater.

Although mixing can be carried out at room temperatures without heating,when solid components are employed, mixing may be carried out whileheating.

Furthermore, the transparent liquid composition for cosmetics of thepresent invention can optionally include medicinal components,antiseptics, coloring agent, and perfumes, wetting agent, anti-oxidants,ultraviolet absorbents, granules such as a scrubbing material, ethanol,water-soluble or oil-soluble high molecular weight compound in order togive a viscous property to the composition, a cationic material in orderto give a conditioning effect to hair, etc. which are conventionallyemployed as additives for cosmetics.

The transparent liquid composition for cosmetics of the presentinvention can be used for cleansings, an agent for massage, an agent forpack, cosmetics for hair, cosmetics for bathroom, cosmetics for keepingmoisture, and a base material for a medicine, etc.

According to a ninth aspect of the present invention, there is provideda gel-like emulsified composition for cosmetics which comprisesglycerine, liquid oily components, a polyvalent alcohol exceptglycerine, and a fatty acid esters composition of a polyglycerine in thefirst aspect or a highly-purified fatty acid esters composition of apolyglycerine in the fourth aspect.

In the ninth aspect of the present invention, there is more preferablyemployed a highly-purified fatty acid esters composition of apolyglycerine in the fourth aspect from viewpoint of the use for humanbody.

In the gel-like emulsified composition for cosmetics of the presentinvention, glycerine is an essential component. Glycerine is employed inan amount ranging from 20 to 60% by weight, preferably from 30 to 60%,and more preferably from 35 to 45% by weight based on the total weightof the gel-like emulsified composition for cosmetics of the presentinvention.

In the case when it is below 20%, a feel in use is deteriorated and, onthe contrary, in the case when it exceeds 60%, a feel in use isdeteriorated because of a warmish feel.

As the liquid oily components, there are specifically employed ahydrocarbon oil such as a liquid paraffin and squalane, an ester oilsuch as cetyl octanate and isopropyl myristate, and a fatty acidtriglyceride such as trioctanic acid triglyceride and olive oil, etc.

Liquid oils primarily containing higher alcohols and higher fatty acidsare not preferred because of instability at high temperatures.

As the polyvalent alcohol except glycerine, there are specificallyemployed propyleneglycol, 1,3-butylene glycol, maltitol, and sorbitol,etc. Of those, there are preferably employed propyleneglycol and1,3-butylene glycol.

The polyvalent alcohol except glycerine are employed in an amountranging from 0.5 to 10% by weight, and preferably from 1 to 5% by weightbased on the total weight of the gel-like emulsified composition forcosmetics of the present invention.

In the gel-like emulsified composition for cosmetics, the fatty acidesters composition of a polyglycerine or the highly-purified fatty acidesters composition of a polyglycerine is employed in an amount rangingfrom 1.0 to 6.0% by weight, preferably from 2.0 to 5.0%, and morepreferably approximately 3.5% by weight based on the total weight of thegel-like emulsified composition for cosmetics of the present invention.

HLB value is preferably more than 11 in the fatty acid esterscomposition of a polyglycerine or the highly-purified fatty acid esterscomposition of a polyglycerine. Of those, there are preferably employeddecaglyceryl monolaurate and hexaglyceryl monolaurate having HLB valueof 11 to 15.

The gel-like emulsified composition for cosmetics of the presentinvention can be used for cleansings and cosmetics for massage, etc.

Furthermore, the gel-like emulsified composition for cosmetics of thepresent invention can optionally include ultraviolet absorbents,antiseptics, anti-oxidants, coloring agent, perfumes, and medicinalcomponents, etc. which are conventionally employed as additives forcosmetics or toiletries.

According to a tenth aspect of the present invention, there is provideda composition for tooth paste which comprises an abrasive, a cakingmaterial, a wetting agent, and a fatty acid esters composition of apolyglycerine in the first aspect or a highly-purified fatty acid esterscomposition of a polyglycerine in the fourth aspect.

In the tenth aspect of the present invention, there is more preferablyemployed a highly-purified fatty acid esters composition of apolyglycerine in the fourth aspect from viewpoint of the use for humanbody.

In the composition for tooth paste, the fatty acid esters composition ofa polyglycerine or the highly-purified fatty acid esters composition ofa polyglycerine is employed in an amount ranging from 0.4 to 10% byweight, preferably from 1.0 to 3.0%, and more preferably approximately2.0% by weight based on the total weight of the composition for toothpaste of the present invention. It is to be noted that the fatty acidesters composition of a polyglycerine or the highly-purified fatty acidesters composition of a polyglycerine acts as a foaming agent.

The composition for tooth paste of the present invention includes apaste, powder, ointment, and liquid type tooth polisher.

As the abrasives, there are included calcium secondary phosphate(dihydrate, anhydride), calcium carbonate, silicates, and insolublesodium metaphosphates.

As the caking material, there are included sodium carboxy-methylcellulose, carrageenan, sodium alginate, bentonite, and silicateanhydride, etc.

As the wetting agent, there are included glycerine, sorbitol,propyleneglycol, sodium pyrrolidone-carboxylate, and polyethyleneglycol,etc.

The composition for tooth paste of the present invention may include avariety of perfumes and medicinal components.

As the medicinal components to be employed, fluorides, glycyrrhizinate,chlorohexydine, hinokitiol, dextranase, lysozyme, edible salts,tranexamic acid, and epsilon-aminocaproic acid, etc. which areconventionally employed for a tooth paste composition.

According to an eleventh aspect of the present invention, there isprovided a cleaning agent composition which comprises (a) apolycarboxylic acid ester of a monoglyceride or a salt thereofrepresented by general formula [3]

R1—COO—CH₂—CHOZ1—CH₂OZ2  [3]

wherein R1 is an alkyl or alkenyl group having a carbon number rangingfrom 7 to 17, either Z1 or Z2 is a residual group of a polycarboxylicacid or salt thereof, and another hydrogen atom or a residual group of apolycarboxylic acid or salt thereof, (b) a fatty acid esters compositionof a polyglycerine in the first aspect or a highly-purified fatty acidesters composition of a polyglycerine in the fourth aspect, (c) organicor inorganic builders, (d) fluidity improvers, and additionally (e)thickening agents, (f) perfumes, (g) coloring agents, (h) sterilizers,(i) enzymes, and (j) anti-inflammatory agents.

In the cleaning agent composition, the component (b) which is the fattyacid esters composition of a polyglycerine or the highly-purified fattyacid esters composition of a polyglycerine is employed in an amountranging from 1.0 to 10.0% by weight, preferably from 2.0 to 8.0%, andmore preferably approximately 5% by weight based on the total weight ofthe cleaning agent composition.

In the case when the amount is below 1.0% by weight, cleaning abilitybecomes poor and, on the contrary, even in the case when the amountexceeds 10.0% by weight, cleaning ability does not increase.

In the cleaning agent composition, the component (a) which is thepolycarboxylic acid ester of a monoglyceride or a salt thereof isrepresented by the general formula [3].

In the formula [3], R1 is an alkyl or alkenyl group having a carbonnumber ranging from 7 to 17 which may be linear or branched.Specifically there are included heptyl group, nonyl group, undecylgroup, tridecyl group, pentadecyl group, heptadecyl group, heptadecenylgroup, etc. Of those, nonyl group, undecyl group, and tridecyl group arepreferably employed from viewpoint of cleaning ability.

Z1 or Z2 is a residual group of a polycarboxylic acid or salt thereof,and another hydrogen atom or a residual group of a polycarboxylic acid.Specifically there are preferably employed citric acid, succinic acid,maleic acid, malic acid, glutaric acid, adipic acid, tartaric acid,diacetyl tartaric acid, and the salts thereof. Of those, there are morepreferably employed citric acid, succinic acid, diacetyl tartaric acid,and the salts thereof.

As the salts, there are included alkali salts such as sodium salts,potassium salts, lithium salts, alkali earth metal salts such asmagnesium salts, ammonium salts, lower amine salts such astrimethylamine, triethylamine salts, lysine salts, mono-, di-, andtri-lower alkanol amine salts such as monoethanol amine, diethanolamine, and triethanol amine which are substituted or non-substitutedammonium salts.

Furthermore, an acid type of the polycarboxylic acid esters of amonoglyceride or the salts thereof exhibits an effect capable ofdecreasing microorganisms in starting materials for processed foods. Onthe other hand, the salts thereof exhibits high cleaning ability.Accordingly, those are preferably employed by appropriately mixing.

Still further, the polycarboxylic acid esters of a monoglyceride or thesalts may contain a position isomer in which the polycarboxylic acidconnects to primary or secondary hydroxyl group in the monoglyceride andcompounds in which 2 mol of the polycarboxylic acid connects to themonoglyceride. It is to be noted that the position isomer and thecompounds are produced in a refining process.

In the cleaning agent composition, the components (a)/(b) are employedin a weight ratio ranging from 90/10 to 30/70, and preferably from 80/20to 40/60.

In the case when the ratio is below 30/70 or exceeds 90/10, cleaningability unpreferably decreases.

Furthermore, the cleaning agent composition of the present invention canoptionally include other additives which are conventionally employed, asfar as cleaning ability is not deteriorated.

As the other additives, there are employed a sodium phosphate of apolyoxyethylene alkylether, a fatty acid ester of sucrose, a fatty acidester of polyoxyethylene sorbitan, a fatty acid monoethanolamide, apolyoxyethylene alkylether, a polyoxyethylene alkylphenylether, acarboxybetaine type-, a imidazolinium type-, a sulphobetaine type-, andan alanine type-surface active agents which are harmless to human body.

As the other additives, there are further employed organic builders suchas sodium pyrophosphate, sodium tripolyphosphate, zeolite, sodiumcitrate, sodium malate, nitrilotrisodium acetate, and a sodiumpolyacrylate, inorganic builders such as sodium carbonate, sodiumsulphate, sodium chloride, magnesium sulphate, and calcium chloride,fluidity improvers such as glycerine, ethanol, propylene glycol, and apolyethyleneglycol, thickening agents such as carboxymethyl celluloseand hydroxyethyl cellulose, perfumes, coloring agents, sterilizers,enzymes, and anti-inflammatory agents, etc.

According to a twelfth aspect of the present invention, there isprovided a foaming composition for cleaning which comprises a mixturecomposed of at least one of a lower monovalent alcohol having a carbonnumber ranging from 1 to 3, water, at least one of a higher alcoholhaving a carbon number ranging from 12 to 22, and a fatty acid esterscomposition of a polyglycerine as set forth in claim 1 or ahighly-purified fatty acid esters composition of a polyglycerine as setforth in claim 14, and an agent for foaming the mixture.

In the foaming composition for cleaning, the fatty acid esterscomposition of a polyglycerine or the highly-purified fatty acid esterscomposition of a polyglycerine is employed in an amount ranging from 0.5to 10.0% by weight, and preferably from 1.0 to 5.0% based on the totalweight of the foaming composition for cleaning.

In the case when the amount is below 0.5% by weight, foaming abilitybecomes poor and, on the contrary, in the case when the amount exceeds10.0% by weight, foaming ability does not only increase but also foam isnot readily broken, and a feel in use becomes worse.

As the lower monovalent alcohol having a carbon number ranging from 1 to3, there are employed methanol, ethanol, n-propanol, and iso-propanol.Of those, ethanol modified by brucine, etc. from viewpoint of innoxiousproperties.

In the foaming composition for cleaning, the lower monovalent alcoholhaving a carbon number ranging from 1 to 3 is employed in an amountranging from 20 to 70% by weight, and preferably from 30 to 60% byweight based on the total weight of the foaming composition forcleaning.

In the case when the amount is below 20% by weight, a refreshing feel inuse becomes not only insufficient but also cleaning ability for fattydirt on skin is insufficient and, on the contrary, in the case when theamount exceeds 70% by weight, durability of foam becomes not only worsebut also a feel in use becomes unpreferably worse.

As the higher alcohol having a carbon number ranging from 12 to 22,there are employed lauryl alcohol, myristyl alcohol, palmityl alcohol,stearlyl alcohol, oleyl alcohol, cetyl alcohol, and behenyl alcohol.

The higher alcohol having a carbon number ranging from 12 to 22 isemployed in an amount ranging from 0.5 to 5% by weight, and preferablyfrom 1 to 3% by weight based on the total weight of the foamingcomposition for cleaning. In the case when the amount is below 0.5% byweight, foaming ability and stability of foam are insufficient and, onthe contrary, in the case when the amount exceeds 5% by weight,stability of the composition and sol therefrom becomes not only worsebut also a feel in use becomes unpreferably worse.

As the agent for foaming the mixture, there are employed liquifiedpetroleum gases such as propane, n-butane, i-butane, n-pentane,i-pentane, and a mixture thereof with dimethylether.

The agent for foaming the mixture is employed in an amount ranging from2 to 15% by weight, and preferably from 3 to 10% by weight based on thetotal weight of the foaming composition for cleaning. In the case whenthe amount is below 2% by weight, foaming ability is insufficient and,contrarily, in the case when the amount exceeds 15% by weight, qualityand stability of foam become worse, and a feel in use becomesunpreferably worse.

The foaming composition for cleaning of the present invention is anaerosol type, and may be a gas/liquid two phases type orgas/liquid/liquid three phases type.

Furthermore, the foaming composition for cleaning of the presentinvention can optionally include polyvalent alcohols, high molecularcompounds, polysaccharides, protein derivatives, extracts from plants,ultraviolet ray absorbents, medicinal components, chelating agents,anti-oxidants, and perfumes as far as effects are not deterioratedwithin an appropriate quantity and quality depending upon purposes.

As the polyvalent alcohols, there are specifically employed propyleneglycol, 1,3-butyleneglycol, dipropylene glycol, glycerine, diglycerine,sorbitan, sorbitol, maltitol, glucose, sucrose, etc.

As the high molecular compounds, there are specifically employed acationic polymer such as poly(dimethyldiallyl ammoniumhalide) [eg.Merquat 100, etc.], a copolymer of dimethyldiallyl ammoniumhalide withan acrylic monomer [eg. Merquat 550, etc. ], a condensate ofpolyethyleneglycol/epichlorohydrin/propyleneamine [Polyquat H, etc.], aquaternary nitrogen-containing cellulose [Polymer JR, etc.], an anionicpolymer such as xanthane gum, carrageenan, sodium alginate, arabic gum,pectic substances, a carboxyvinyl polymer, a nonionic polymer such as acopolymer of vinyl acetate with polyvinyl pyrrolidone, or vinylpyrrolidone, a copolymer of vinyl pyrrolidone with vinyl acetate and anacrylicaminoacrylate, hydroxyethylcellulose, hydroxypropylcellulose,hydroxypropyl ethylcellulose, methylcellulose, dextrins, galactan,pullulan, amphoretic polyelectrolytes such as Yukafoamer AM-75 in whichthere are copolymerized dialkylaminoethlacrylate,dialkylaminoethylmethacrylate, and diacetone acrylamide withalkylacrylates or alkylmethacrylates, and then modified by acetichalides.

As the polysaccharides, there are specifically employed hyaluronic acid,chondroitin, heparan sulphate, and salts thereof.

As the ultraviolet ray absorbents, there are specifically employedparaaminobenzoic acid, glycerylparraminobenzoic acid,etihyldihydroxypropylparaaminobenzoic acid, etc.

As the medicinal components, there are specifically employed vitamin C,vitamin Es, amino acids, anti-inflammatory agent, and sterilizers, etc.

The present invention is illustrated below by Examples and ComparativeExamples.

EXAMPLE 1

Preparation No. 1 of a Fatty Acid Esters Composition of a PolyglycerineContaining More than 70% of a Fatty Acid Monoester

A four-necked reaction vessel equipped with a tube for supplyingnitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise funnelwas charged with 100.16 parts by weight of lauric acid and 0.0622 partby weight of phosphoric acid (a purity of 85%), followed by heating to140° C. Subsequently, 222.24 parts by weight (molar ratio ofglycidol/lauric acid=6) of glycidol was added drowpwise over 5 hours toallow to react until oxirane oxygen concentration in the reactantattains below 0.1% while maintaining the reaction temperature at 140° C.

After cooling, the reactant was taken out to obtain approximately 300parts by weight of a lauric acid esters composition of a polyglycerine.The lauric acid esters composition of a polyglycerine prepared wasanalyzed by the HPLC analytical condition No. 1 as defined hereinabove.

The lauric acid esters composition of a polyglycerine (hereinafter,referred to as PGMLEC) prepared was dissolved in water to prepare anaqueous solution of 10%, followed by vibrating with hands for 30 secondsto visually observe foaming ability and appearance.

FIG. 1 is a chart obtained by the HPLC analysis relating to the PGMLECprepared. It was identified from the chart that the composition (ahexaglycerine monolaurate composition) contains a monolaurate ofpolyglycerine of 87.7% analyzed by the condition No. 1 in the HPLCanalysis method.

EXAMPLE 2

Preparation No. 2 of a Fatty Acid Esters Composition of a PolyglycerineContaining More than 70% of a Fatty Acid Monoester

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with100.16 parts by weight of lauric acid and 0.0810 part by weight ofphosphoric acid (85%), followed by heating to 140° C.

Subsequently, 222.24 parts by weight (molar ratio of glycidol/lauricacid=6) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C. After cooling, thereactant was taken out to obtain approximately 300 parts by weight of alauric acid esters composition of a polyglycerine. The lauric acidesters composition of a polyglycerine prepared was analyzed by the HPLCanalytical conditions described hereinabove.

The lauric acid esters composition of a polyglycerine (PGMLEC) preparedwas dissolved in water to prepare an aqueous solution of 10%, followedby vibrating with hands for 30 seconds to visually observe foamingability and appearance.

FIG. 2 is a chart obtained by the HPLC analysis relating to PGMLECprepared. It was identified from the chart that the composition (ahexaglycerine monolaurate composition) contains a monolaurate ofpolyglycerine of 90.8% analyzed by the condition No. 1 in HPLC analysismethod.

EXAMPLE 3

Preparation No. 3 of a Fatty Acid Esters Composition of a PolyglycerineContaining More than 70% of a Fatty Acid Monoester

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with100.16 parts by weight of lauric acid and 0.0622 part by weight ofphosphoric acid (85%) followed by heating to 140° C.

Subsequently, 296.32 parts by weight (molar ratio of glycidol/lauricacid=8) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C. After cooling, thereactant was taken out to obtain approximately 400 parts by weight of alauric acid esters composition of a polyglycerine. The lauric acidesters composition of a polyglycerine prepared was analyzed by the HPLCanalytical condition No. 1 as described hereinabove.

The lauric acid esters composition of a polyglycerine (PGMLEC) preparedwas dissolved in water to prepare an aqueous solution of 10%, followedby vibrating with hands for 30 seconds to visually observe foamingability and appearance.

FIG. 3 is a chart obtained by HPLC relating to PGMLEC prepared. It wasidentified from the chart that the composition (an octaglycerinemonolaurate composition) contains a monolaurate of polyglycerine of84.5% analyzed by the condition No. 1 in HPLC analysis method.

EXAMPLE 4

Preparation No. 4 of a Fatty Acid Esters Composition of a PolyglycerineContaining More than 70% of a Fatty Acid Monoester

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with100.16 parts by weight of lauric acid and 0.118 part by weight ofphosphoric acid (85%), followed by heating to 140° C.

Subsequently, 370.40 parts by weight (molar ratio of glycidol/lauricacid=10) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C. After cooling, thereactant was taken out to obtain approximately 470 parts by weight of alauric acid esters composition of a polyglycerine. The lauric acidesters composition of a polyglycerine prepared was analyzed by the HPLCanalytical conditions described hereinabove.

The lauric acid esters composition of a polyglycerine (PGMLEC) preparedwas dissolved in water to prepare an aqueous solution of 10%, followedby vibrating with hands for 30 seconds to visually observe foamingability and appearance.

FIG. 4 is a chart obtained by the HPLC analysis relating to the PGMLECprepared. It was identified from the chart that the composition (adecaglycerine monolaurate composition) contains a monolaurate ofpolyglycerine of 77.2% analyzed by the condition No. 1 in the HPLCanalysis method.

EXAMPLE 5

Preparation No. 5 of a Fatty Acid Esters Composition of a PolyglycerineContaining More than 70% of a Fatty Acid Monoester

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with100.16 parts by weight of lauric acid and 0.105 part of a mixturecomposed of monoethyl acid phosphate and diethyl acid phosphate (EAPmanufactured by Nihon Kagaku Kogyo, Ltd.), followed by heating to 140°C.

Subsequently, 370.04 parts by weight (molar ratio of glycidol/lauricacid=10) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C. After cooling, thereactant was taken out to obtain approximately 470 parts by weight of alauric acid esters composition of a polyglycerine. The lauric acidesters composition of a polyglycerine prepared was analyzed by the HPLCanalytical condition No. 1 as described hereinabove.

The lauric acid esters composition of a polyglycerine (PGMLEC) preparedwas dissolved in water to prepare an aqueous solution of 10%, followedby vibrating with hands for 30 seconds to visually observe foamingability and appearance.

FIG. 5 is a chart obtained by the HPLC analysis relating to the PGMLECprepared. It was identified from the chart that the composition (adecaglycerine monolaurate composition) contains a monolaurate ofpolyglycerine of 77.2% analyzed by the condition No. 1 in HPLC analysismethod.

Comparative Example 1

Preparation in the Absence of Catalysts

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with100.16 parts by weight of lauric acid, followed by heating to 140° C.

Subsequently, 222.24 parts by weight (molar ratio of glycidol/lauricacid=6) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C. After cooling, thereactant was taken out to obtain approximately 300 parts by weight of alauric acid esters composition of a polyglycerine. The lauric acidesters composition of a polyglycerine prepared was analyzed by the HPLCanalytical condition No. 1 as described hereinabove.

The lauric acid esters composition of a polyglycerine (PGMLEC) preparedwas dissolved in water to prepare an aqueous solution of 10%, followedby vibrating with hands for 30 seconds to visually observe foamingability and appearance.

FIG. 6 is a chart obtained by the HPLC analysis relating to the PGMLEC(a hexaglycerine monolaurate composition) prepared.

Comparative Example 2

Preparation in the Presence of Paratoluene Sulfonic Acid

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with100.16 parts by weight of lauric acid and 0.371 part by weight ofparatoluene sulfonic acid as a catalyst, followed by heating to 140° C.Subsequently, 222.24 parts by weight (molar ratio of glycidol/lauricacid=6) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C. After cooling, thereactant was taken out to obtain approximately 300 parts by weight of alauric acid esters composition of a polyglycerine.

The lauric acid esters composition of a polyglycerine prepared wasanalyzed by the HPLC analytical conditions described hereinabove. Thelauric acid esters composition of a polyglycerine (PGMLEC) prepared wasdissolved in water to prepare an aqueous solution of 10%, followed byvibrating with hands for 30 seconds to visually observe foaming abilityand appearance.

FIG. 7 is a chart obtained by the HPLG analysis relating to the PGMLEC(a hexaglycerine monolaurate composition) prepared.

Comparative Example 3

Preparation by the Reaction of a Fatty Acid Monoglyceride with Glycidol

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with137 parts by weight monoglyceride of lauric acid and 0.45 part by weightof sodium methylate (methanol solution having 28%) as a catalyst,followed by heating to 90° C.

Subsequently, 185.2 parts by weight (molar ratio ofglycidol/monoglyceride of lauric acid=5) of glycidol was added drowpwiseover 5 hours to allow to react until oxirane oxygen concentration in thereactant attains below 0.1% while maintaining the reaction temperatureat 140° C. After cooling, the reactant was taken out to obtainapproximately 300 parts by weight of a lauric acid esters composition ofa polyglycerine.

The lauric acid esters composition of a polyglycerine prepared wasanalyzed by the HPLC analytical condition No. 1 as describedhereinabove.

The lauric acid esters composition of a polyglycerine (PGHLEC) preparedwas dissolved in water to prepare an aqueous solution of 10%, followedby vibrating with hands for 30 seconds to visually observe foamingability and appearance.

FIG. 8 is a chart obtained by the HPLC analysis relating to the PGMLECprepared.

Comparative Example 4

Preparation by the Reaction of a Fatty Acid with Polyglycerine

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with175.3 parts by weight a polyglycerine having a hydroxyl value of 960(PGL06/a hexaglycerine manufactured by Daicel Chemical Industries, Ltd.,followed by heating to 80° C. Subsequently, 100.16 parts by weight(molar ratio of polyglycerine/lauric acid=1) of lauric acid wasdissolved while maintaining at 80° C.

Subsequently, 0.75 part by weight of sodium carbonate and 0.25 part byweight of sodium hydrosulphite were added to allow to react byesterification at 210° C. After two hours, acid value was changed to0.89, followed by taking out a reaction product after cooling at 100° C.

The lauric acid esters composition of a polyglycerine prepared wasanalyzed by the HPLC analytical conditions described hereinabove. It wasidentified from the chart that the lauric acid esters composition of apolyglycerine prepared (a hexa glycerine monolaurate composition)contains a monolaurate of polyglycerine of 55.1%.

The composition was dissolved in water to prepare an aqueous solution of10%, followed by vibrating with hands for 30 seconds to visually observefoaming ability and appearance.

FIG. 9 is a chart obtained by the HPLC analysis relating the PGMLECprepared. Results are shown in Table 1.

TABLE 1 Examples Comparative Example 1 2 3 4 5 1 2 3 4 A 6 6 8 10 10 1010 10 8 B 12 12 12 12 12 12 12 12 12 C (1) 87.7 90.8 84.5 77.2 77.2 53.152.2 44.3 55.1 (2) 3.0 2.8 11.0 15.0 15.0 4.4 5.7 12.0 17.6 (3) 9.3 6.44.5 7.5 7.5 42.5 42.1 43.7 27.3 D Ex Ex Ex Ex Ex P P P P E SW SW SW SWSW W W W W F FY FY FY FY FY Y Y Y Y G T T T T T T T T T H O O O O O O OO O

Comparative Examples 5 to 14

Evaluation of Fatty Acid Esters Composition of a Polyglycerine which areCommercially Supplied

Fatty acid esters composition of a polyglycerine which is prepared bythe reaction of a polyglycerine with a fatty acid was evaluated byvisually observing relating to foaming ability and appearances similarlyto Examples.

Furthermore, the lauric acid esters composition of a polyglycerineprepared was analyzed by the HPLC analysis similarly to Examples. FIGS.10 to 19 are charts obtained by the HPLC analysis No. 1 as describedhereinabove relating to the PGMLEC prepared, respectively.

Results are shown in Table 2.

TABLE 2 Comparative Example 5 6 7 8 9 10 11 12 13 14 PG (1) (2) (3) (4)(5) (6) (7) (8) (9) (10) A 4 10 4 6 10 6 10 6 6 10 B 8 8 12 12 12 12 128 12 12 C (1) 50.0 41.5 47.5 52.0 44.3 65.5 53.1 53.2 52.2 55.1 (2) 2.04.1 1.4 6.8 12.0 3.8 4.4 3.8 5.7 17.6 (3) 48.0 54.4 51.1 41.2 43.7 30.742.5 43.0 42.1 27.3 D P P P P SP SP Ex P P Ex E W W W W SW SW SW W W SWF Y Y Y Y Y FW FY FY FW FW G T T T T T T T T T T H O O O O O O O O O O

In the Tables 1 and/or 2, alphabetical abbreviations and numbering areas follows.

PG: fatty acid esters composition of a polyglycerine commerciallysupplied

(1): SY Glystar MO-310 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

(2): SY Glystar MO-750 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

(3): SY Glystar ML-310 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

(4): SY Glystar ML-500 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

(5): SY Glystar MO-750 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

(6): Poem J-6021 manufactured by Riken Vitamin, Ltd.

(7): Poem J-0021 manufactured by Riken Vitamin, Ltd.

(8): Unigly GO-106 manufactured by Nihon Yushi, Ltd.

(9): Unigly GL-106 manufactured by Nihon Yushi, Ltd.

(10): Sunsoft Q12S manufactured by Taiyo Kagaku, Ltd.

A: the number of glycerine unit (pieces)

B: the carbon number of fatty acid

C: peak area ratio by HPLC (UV)

(1): fatty acid mono ester

(2): polyglycerine

(3): others

D: foaming ability (visual observation after vibration with hands for 30seconds relating to 10% aqueous solution)

Ex: excellent

P: poor

E: appearance (at standing still 10% aqueous solution)

SW: slightly whitening

W: whitening

F: color hue

FW: faintly white

FY: faintly yellow

Y: yellow

G: appearance (at heating)

T: transparent

H: appearance (at room temperatures)

O: opaque

EXAMPLE 6

Preparation No. 1 of a Highly-purified Fatty Acid Esters Composition ofa Polyglycerine

First Step

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with100.16 parts by weight of lauric acid and 0.0622 part by weight ofphosphoric acid (a purity of 85%) followed by heating to 140° C. whilestirring.

Subsequently, 222.24 parts by weight (molar ratio of glycidol/lauricacid=6) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 670 ppmwhile maintaining the reaction temperature at 140° C. to obtain aproduct. An acid value of the product obtained in the first step was0.13 (JIS 1557).

Furthermore, it was identified that the product (a hexaglycerinemonolaurate composition) contains a monolaurate of polyglycerine of87.7%.

Still further, the product was analyzed by the proton NMR in whichmethanedeuterium chloride was employed as a solvent, the solutionconcentration of the product was approximately 5%, temperature formeasuring is 40° C., and JOEL270Mz (manufactured by Nihon Denshi, Ltd.).Results are shown in Tables 20 and 21.

From the proton NMR analysis, it is identified that peak area of achemical shift between 2.7 ppm and 2.8 ppm assigned by methylene protonin oxirane group is 0.5, and peak area of a chemical shift between 3.4ppm and 4.4 ppm assigned by methylene proton in polyglycerine andmethine proton is 962.6. Peak area ratio is (0.551/962.6)×100=0.52(%).

It is to be noted that the number 0.551 corresponds to 1.655/3 in whichthe denominator 3 corresponds to 3 protons (a, b, and c), and thenumerator 1.655 corresponds to peak area of 3 protons (a, b, and c).

Second Step

After the completion of the first step, water was added into the flaskin the amount of 2% by weight based on the product, followed by heatingto 135° C. while stirring.

Subsequently, the temperature was maintained while refluxing for 2hours, followed by raising the temperature to 140° C. Subsequently,distillation was carried out to remove water in a reduced pressure whilemaintaining the temperature at 140° C.

Reduced pressure degree after 4 hours distillation was 10 mmHg. Oxiraneoxygen concentration and acid value in a highly-purified fatty acidesters composition of a polyglycerine obtained were 72 ppm and 0.45,respectively.

Still further, the product was analyzed by the proton NMR similarly tothe first step.

Results are shown in Tables 22 and 23.

From the proton NMR analysis, it is identified that peak area of achemical shift between 2.7 ppm and 2.8 ppm assigned by methylene protonin oxirane group is not observed.

Accordingly, peak area ratio is zero.

EXAMPLE 7

Preparation No. 2 of a Highly-purified Fatty Acid Esters Composition ofa Polyglycerine

First Step

Same procedures were repeated as in Example 6

Second Step

After the completion of the first step, water was added into the flaskin the amount of 2% by weight based on the product, followed by heatingto 120° C. while stirring.

Subsequently, the temperature was maintained while refluxing for 6hours, followed by raising the temperature to 140° C. Subsequently,distillation was carried out to remove water in a reduced pressure whilemaintaining the temperature at 140 C.

Reduced pressure degree after 4 hours distillation was 10 mmHg. Oxiraneoxygen concentration and acid value in a highly-purified fatty acidesters composition of a polyglycerine obtained were 260 ppm and 0.45,respectively.

EXAMPLE 8

Preparation No. 3 of a Highly-purified Fatty Acid Esters Composition ofa Polyglycerine

First Step

Same procedures were repeated as in Example 6

Second Step

After the completion of the above-described first step, water was addedinto the flask in the amount of 2% by weight based on the product,followed by heating to 120° C. while stirring. Subsequently, thetemperature was maintained while refluxing for 2 hours, followed byraising the temperature to 140° C. Subsequently, distillation wascarried out to remove water in a reduced pressure while maintaining thetemperature at 140° C.

Reduced degree after 4 hours distillation was 10 mmHg.

Oxirane oxygen concentration and acid value in a highly-purified fattyacid esters composition of a polyglycerine obtained were 430 ppm and0.45, respectively.

EXAMPLE 9

Preparation No. 4 of a Highly-purified Fatty Acid Esters Composition ofa Polyglycerine

First Step

Same procedures were repeated as in Example 6

Second Step

After the completion of the first step, water was added into the flaskin the amount of 2% by weight based on the product, followed by heatingto 140° C. while stirring.

Subsequently, the temperature was maintained while refluxing for 2hours. Subsequently, distillation was carried out to remove water in areduced pressure while maintaining the temperature. Reduced pressuredegree after 4 hours distillation was 10 mmHg. Oxirane oxygenconcentration and acid value in a highly-purified fatty acid esterscomposition of a polyglycerine obtained were 72 ppm and 0.45,respectively.

It is to be noted that in Examples from 6 to 9, the concentration valueof oxirane oxygen in the fatty acid esters composition of apolyglycerine was analyzed according to the titration method defined inCd. 9-57 of Journal of American Oil Chemists' Society, and it is to benoted that in Examples and Comparative Examples, acid value was analyzedaccording to JIS 1557.

EXAMPLE 10

Preparation No. 1 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for a Thermoplastic Resin

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with284.49 parts by weight of stearic acid and 0.0622 part by weight ofphosphoric acid (a purity of 85%), followed by heating to 140° C.Subsequently, 222.24 parts by weight (molar ratio of glycidol/stearicacid=6) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140°C., to obtainapproximately 500 parts by weight of a fatty acid esters composition ofa polyglycerine (hexaglycerine monostearate composition).

EXAMPLE 11

Preparation No. 2 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for a Thermoplastic Resin

Same procedures were repeated as in Example 10 except that 296.32 partsby weight (molar ratio of glycidol/stearic acid=8) of glycidol wasemployed to obtain approximately 575 parts by weight of a fatty acidesters composition of a polyglycerine (octaglycerine monostearatecomposition).

EXAMPLE 12

Preparation No. 3 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for a Thermoplastic Resin

Same procedures were repeated as in Example 10 except that 100.16 partsby weight (molar ratio of glycidol/lauric acid=6) of lauric acid wasemployed to obtain approximately 320 parts by weight of a atty acidesters composition of a polyglycerine (hexaglycerine monolauratecomposition).

EXAMPLE 13

Preparation No. 4 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for a Thermoplastic Resin

Same procedures were repeated as in Example 12 except that 296.32 partsby weight (molar ratio of glycidol/lauric acid=8) of glycidol wasemployed to obtain approximately 390 parts by weight of a fatty acidesters composition of a polyglycerine (octaglycerine monolauratecomposition).

Application Examples 1-4 and Comparative Application Examples 1-3

The use of Products Obtained on Examples 10-13 as an Anti-static Agentfor a Thermoplastic Resin

There was prepared a mixture composed of 100 parts by weight of apolyvinyl chloride (a homopolymer having a polymerization degree of700), 1.0 part by weight of a mercapt tinoctylate-based stabilizer, 2.0parts by weight of an epoxidized soy bean oil, 0.5 part by weight ofstearic acid, and 10 part weight of a reinforced material.

4 parts by weight of respective products obtained in Examples 10-13 andcommercially supplied fatty acid esters of polyglycerine as shown inTable 3 were mixed with the mixture to obtain respective films by acalendar process, followed by being biaxially-two fold oriented toobtain films having the thickness of 30 microns. There were measuredsurface resistance, transparency, and workability in the calendarprocess of the oriented films. Transparency was evaluated based on Haizevalue.

Results are shown in Table 3.

TABLE 3 Resistance Trans- Surface (ohm) parency Workability ApplicationExamples 1 A 3.0 × 10¹² very good very good 2 B 2.0 × 10¹² very goodvery good 3 C 1.0 × 10¹² very good very good 4 D 1.0 × 10¹² very goodvery good Comparative Application Examples 1 E 5.0 × 10¹³ good slightlygood 2 F 3.0 × 10¹³ good slightly good 3 G 5.0 × 10¹⁴ good slightly good

In the Table 3, A, B, C, and D correspond to respective productsobtained in Examples 10, 11, 12, and 13, respectively, and E, F, and Gcorrespond to SY-GLYSTAR-MS-500, SY-GLYSTAR-ML-500 manufactured bySakamoto Yakuhin, Ltd., and a glycerine monostearate, respectively.

EXAMPLE 14

Preparation No. 4 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for a Thermoplastic Resin

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with100.16 parts by weight of lauric acid and 0.0622 part by weight ofphosphoric acid (a purity of 85%) followed by heating to 140° C.Subsequently, 222.24 parts by weight (molar ratio of glycidol/lauricacid=6) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C. for 26 hours, toobtain approximately 300 parts by weight of a fatty acid esterscomposition of a polyglycerine (a hexaglycerine monolauratecomposition). Content of the monoester was 87.7% based on the HPLCanalytical condition No. 1 as described hereinabove.

EXAMPLE 15

Preparation No. 5 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for a Thermoplastic Resin

Same procedures were repeated as in Example 14 except that 296.32 partsby weight (molar ratio of glycidol/lauric acid=8) of glycidol wasemployed to obtain approximately 400 parts by weight of a fatty acidesters composition of a polyglycerine (an octaglycerine monolauratecomposition).

Content of the monoester was 84.5% based on the HPLC method describedhereinabove.

EXAMPLE 16

Preparation No. 6 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for a Thermoplastic Resin

Same procedures were repeated as in Example 14 except that 370.40 partsby weight (molar ratio of glycidol/lauric acid=10) of glycidol wasemployed to obtain approximately 470 parts by weight of a fatty acidesters composition of a polyglycerine (a decaglycerine monolauratecomposition).

Content of the monoester was 77.2% based on the HPLC analyticalcondition No. 1 as described hereinabove.

Comparative Example 1

Preparation No. 7 of a Fatty Acid Esters Composition of a Polyglycerinenot Derived from Glycidol as an Additive for a Thermoplastic Resin

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with175.3 parts by weight of a polyglycerine (PGL06 having a hydroxyl valueof 960 manufactured by Daicel Chemical Industries, Ltd.), followed byheating at 80° C. Subsequently, 100.16 parts by weight (molar ratio ofpolyglycerine/lauric acid=1) of lauric acid was dissolved whilemaintaining 80° C., followed by allowing to react for two hours afteradding 0.75 part by weight of sodium carbonate and 0.25 part by weightof sodium hydrogen sulfite at 210° C. After cooling to 100° C., acidvalue attained 0.89, and a polyglycerine monolaurate compositionprepared was taken out. Content of the monoester was 55.1% based on theHPLC analytical condition No. 1 as described hereinabove.

Application Example 5

Evaluations as an Agent for Improving Anti-static Property of aStyrene-based Resin

100 parts by weight of a styrene-based resin having styrene unit of 100%was mixed with 4.0 parts by weight of a hexaglycerine monostearateobtained by Example 1 and 2.0 parts by weight of tristearyl phosphite(JP-318E manufactured by Johoku Kagaku Kogyo, Ltd.) with a HenshelMixer, followed by being pelletized with an extruder having the cylinderdiameter of 40 mm phi (manufactured by Nakaya Kikai).

Pellets were molded by an injection machine (an N70A type manufacturedby Nihon Seiko) equipped with a flat molding die [200L×70W×3t] at thecylinder temperature of 240° C. and the molding die temperature of 50°C.) to prepare flat test pieces.

Maximum-charged voltage was 400V, the half period was 4.2 seconds, andintrinsic surface resistance was 72×10¹² ohm.

It is to be noted that anti-static property of a styrene-based resin wasevaluated by the half period of a maximum charged pressure (NeostmeterS-4104 manufactured by Shishido Syokai), and an intrinsic surfaceresistance (an intrinsic surface resistance meter, TR-8601 manufacturedby Takeda Riken).

Application Example 6

Evaluations as an Agent for Improving Anti-static Property of aStyrene-based Resin

The same procedures as described in Application Example 5 were repeatedexcept that there was further mixed 2.0 parts by weight of apolyethyleneglycol having a molecular weight of 300.

Maximum-charged voltage was 380V, the half period was 3.2 seconds, andintrinsic surface resistance was 56×10¹² ohm.

Application Example 7

Evaluations as an Agent for Improving Anti-static Property of aStyrene-based Resin

The same procedures as described in Example 5 were repeated except thatthere were employed 8.0 parts by weight of a hexaglycerine monostearateobtained by Example 1 and 6.0 parts by weight of a polyethyleneglycolhaving a molecular weight of 1000. Maximum-charged voltage was 380V, thehalf period was 2.2 seconds, and intrinsic surface resistance was38×10¹² ohm.

In the case when the fatty acid esters composition of a polyglycerine ismixed in an amount exceeding 6 parts by weight, although the excellentanti-static property is given to a styrene-based resin, bleeding isunpreferably caused as described hereinabove.

Application Examples 8-11

Evaluations as an Agent for Improving Anti-static Property of aStyrene-based Resin

Same procedures were repeated as in Application Example 5 except thatcomponents were mixed as shown in Table 4.

Comparative Application Examples 4-5

Evaluations as an Agent for Improving Anti-static Property of aStyrene-based Resin

Same procedures were repeated as in Application Example 5 except thatcomponents were mixed as shown in Table 5.

TABLE 4 Application Example 8 9 10 11 Mixing components Styrene basedresin St/MMA St/AN St/MMA/ St/MMA/ MA MA/CHMI Monomer ratio (wt %) 50/5060/40 40/56/4 10/70/5/15 PGLE MS06 MS06 MS06 MS06 (part by weight) (4)(4) (4) (4) Phosphorus compound DP SP DP SP (part by weight) (2) (1) (3)(1) PAG 3E 10E 10P — (part by weight) (0.5) (1) (2) — Properties MCV (v)420 420 440 410 HP (second) 4.02 5.3 4.0 3.9 SIR (×10) 55 72 69 85

TABLE 5 Comparative Application Example 4 5 Mixing componentsStyrene-based resin St/MMA St/MMA Monomer ratio (wt %) 50/50 50/50 PGLEMS06 — (part by weight) (4) — Phosphorus compound — SP (part by weight)— (2) PAG — — Properties MCV (v) 500 540 HP (second) 92 210< SIR (×10¹²)1800 36000

In the Tables 4 and 5, abbreviations are as follows.

St: Styrene

MMA: Methylmethacrylate

AN: Acrylonitrile

MA: Methylacrylate

CHM1: Cyclohexylmaleimide

PGLE: Fatty acid esters composition of a polyglycerine

MS06: Hexaglycerine monostearate obtained in Example 2

DP: Tridecylphosphite

SP: Tristearylphosphite

PAG: Polyalkylene glycol

3E: Polyethylene glycol having a molecular weight of 300

10E: Polyethylene glycol having a molecular weight of 1000

10P: Polypropylene glycol having a molecular weight of 1000

MCV: Maximum-charged voltage

HP: Half period

SIR: Surface intrinsic resistance

It is clearly identified from the values in Tables 4 and 5 that anexcellent anti-static property is given to a styrene-based resin bymixing an appropriate amount of the fatty acid esters composition of apolyglycerine in the present invention.

Application Example 12

Evaluation as a Releasing Agent for Methylmethacrylate-based Resin

There were mixed 100 parts by weight of a particle-state methacrylicresin [Sumipex BLO manufactured by Sumitomo Chemicals Industries, Ltd.],0.025 part by weight of dipentaerythritol tripalmitate, and 0.025 partby weight of the fatty acid esters composition of a polyglycerineobtained in Example 1 with a Henshel Mixer, followed by being extrudedwith a vent-type extruder having the cylinder diameter of 40 mm phi toobtain pellets.

Pellets obtained were molded by a 13-ounces injection machine (anM-140SJ type manufactured by Meiki Seisakusyo) equipped with a moldingdie [25 mm×76.5 mm×3.2 mm] at the cylinder temperature of 260° C.,molding die temperature of 60° C., injection pressure of 80 kg/cm²-G,with interval of 60 seconds to evaluate a releasing property whilecontinuously preparing ASTM test pieces for 40 times.

The releasing property was evaluated by comparing the number of brokenor cracked pieces in the test pieces. Contamination property in themolding die was evaluated by visually observing the presence or absenceof clouding portions in the inner surface of the molding die accordingto the following levels.

N.C: no-clouding

X: clouding

Outer appearance in the test pieces was evaluated by visually observingcontamination or coloring in pieces.

Application Examples 13 to 19

Evaluation as a Releasing Agent for a Methylmethacrylate-based Resin

The same procedures were repeated as described in Application Example 12according to mixing ratio as shown in Table 6.

Comparative Application Examples 6 to 9

Evaluation as a Releasing Agent for a Methylmethacrylate-based Resin

The same procedures were repeated as described in Example 24 accordingto mixing ratio as shown in Table 6.

TABLE 6 mixing ratio RP CP OA Application Example 12 A (0.025)/E (0.025)7.6 NC G 13 A (0.05)/E (0.05) 6.4 NC G 14 A (0.1)/E (0.07) 5.0 NC G 15 A(0.03)/E (0.07) 6.3 NC G 16 A (0.07)/E (0.03) 6.4 NC G 17 B (0.05)/E(0.05) 6.6 NC G 18 C (0.05)/E (0.05) 6.7 NC G 19 D (0.05)/E (0.05) 6.7NC G Comparative Application Example 6 — — 15.0 NC G 7 A (0.1)/ — 12.3NC G 8 — /E (0.1) 12.3 NC G 9 A (0.3)/E (0.3) 4.4 X SY

In the Table 6, abbreviations are as follows.

A: Dipentaerythritol tripalmitate

B: Dipentaerythritol hexabehenate

C: Monopentaerythritol

D: Tripentaerythritol

E: Fatty acid esters composition of a polyglycerine obtained in Example1

RP: Releasing property

CP: Contamination property

OA: Outer appearance

NC: No-clouding

X: Clouding

G: Good

SY: Slightly yellowing

It is clearly identified from the values in Table 5 that an excellentreleasing property is given to a methylmethacrylate-based resin bymixing an appropriate amount of the fatty acid esters composition of apolyglycerine in the present invention.

EXAMPLE 17

Preparation No. 8 of a Fatty Acid Esters Composition of a Polyglycerineas an Agent for Improving Properties of a Thermoplastic Resin

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with284.49 parts by weight of stearic acid and 0.0622 part by weight ofphosphoric acid (a purity of 85%), followed by heating to 140° C.Subsequently, 222.24 parts by weight (molar ratio of glycidol/stearicacid=6) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C.

There was obtained approximately 500 parts by weight of a fatty acidesters composition of a polyglycerine (a hexaglycerine monostearatecomposition). The composition is designated E-1.

EXAMPLE 18

Preparation No. 9 of a Fatty Acid Esters Composition of a Polyglycerineas an Agent for Improving Properties of a Thermoplastic Resin

Same procedures were repeated as in Example 17 except that 296.32 partsby weight (molar ratio of glycidol/stearic acid=8) of glycidol wasemployed to obtain approximately 565 parts by weight of a fatty acidesters composition of a polyglycerine (an octaglycerine monostearatecomposition).

The composition is designated E-2.

EXAMPLE 19 Preparation No. 10 of a Fatty Acid Esters Composition of aPolyglycerine as an Agent for Improving Properties of a ThermoplasticResin

Same procedures were repeated as in Example 17 except that 370.40 partsby weight (molar ratio of glycidol/stearic acid=10) of glycidol wasemployed to obtain approximately 650 parts by weight of a fatty acidesters composition of a polyglycerine (a decaglycerine monostearatecomposition).

The composition is designated E-3.

Comparative Preparation Example 1

Preparation No. 11 of a Fatty Acid Esters Composition Obtained by theReaction of Fatty Acid with a Polyglycerine as an Agent for ImprovingProperties of a Thermoplastic Resin

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with175.3 parts by weight of a hexaglycerine having a hydroxyl value of 960[PGL106 manufactured by Daicel Chemical Industries, Ltd.], followed byheating to 80° C. Subsequently, 100.16 parts by weight (molar ratio ofhexaglycerine/lauric acid=1) of lauric acid was dissolved whilemaintaining at 80° C. Subsequently, 0.75 part by weight of sodiumcarbonate and 0.25 part by weight of sodium hydrogen sulphite wereadded, followed by allowing to react at 210° C. for 2 hours to obtain aproduct. After cooling to ₁₀₀° C., there was taken out the producthaving an acid value of 0.89.

The product was analyzed by the HPLC analytical condition No. 1 asdescribed hereinabove to identify the content of a lauric monoestercompound of polyglycerine (a hexaglycerine monoester composition) of55.1%.

The product is designated E-4.

Comparative Preparation Examples 2 and 3

Measurement of the Content of Monoester Compound in CommerciallySupplied Fatty Acid Esters Composition

As a commercially supplied fatty acid esters composition obtained by thereaction of fatty acid with a polyglycerine, there were evaluated SYGlystar ML-500 and SY Glystar ML-750 (manufactured by Sakamoto YakuhinIndustries).

ML-500 exhibited the content of monoester compound of 52.0%, and ML-750exhibited the content of monoester compound of 44.3%. ML-500 and ML-750are designated E-5 and E-6.

Results are shown in Table 7.

Preparation Example 1

Preparation No. 1 of a Polyacetal Resin

A polyacetal resin in which 2.8% of ethylene oxide is copolymerized wasprepared according to known processes described in U.S. Pat. No.3,027,352.

The polyacetal resin has an intrinsic viscosity of 1.0 (measured with am-chlorophenol solution having 2.0% by weight of alpha-pinene containing0.% by weight of the polyacetal resin at 600° C.) and melt index of 30.0g/10 minutes (according to ASTM D1238-57T). The polyacetal resin isdesignated P-1.

Preparation Example 2

Preparation No. 2 of a Polyacetal Resin

The polyacetal resin having an intrinsic viscosity of 1.2 (measured witha m-chlorophenol solution having 2.0% by weight of alpha-pinenecontaining 0.1% by weight of the polyacetal resin at 60° C.) and meltindex of 40.0 g/10 minutes (according to ASTM D1238-57T) in whichterminals are acetylated was prepared according to known processesdescribed in U.S. Pat. No. 2,998,409.

The polyacetal resin is designated P-2.

Application Examples 20 to 29

Preparation of Articles Molded from a Polyacetal Resin Composition andEvaluations as an Agent for Improving a Printing Property by the FattyAcid Esters Composition of the Present Invention

There were mixed 0.2 part by weight of triethyleneglycolbis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], the above-preparedpolyacetal resins, a hindered amine compound, a fatty acid esterscomposition of a polyglycerine, and a nucleating agent in a mixing ratioas shown in Tables 4 and 5 under a nitrogen atmosphere, followed byextruding with a L/D=25 single screw extruder (the screw revolution of100 rpm and the discharge amount of 6 kg/hour) having a vent to preparepellets.

The pellets were dried, and then molded (the mold temperature of 100° C.and the cooling time of period of 7 seconds) with a 5-ounces moldingmachine to prepare MFD shutters.

The MFD shutters were irradiated by a corona discharging lamp(irradiation energy of 90 watt, irradiation time of 0.2 second,discharging clearance of 7 mm, and discharging rate of 10 mm/sec).Subsequently, an ink (Tampo R double-liquid manufactured by Tampo, Ltd.)was printed on a portion of the surface having slightly more than 1 cmsquare in the respective MFD shutters. Subsequently, curing was carriedout at the heating temperature of 120° C. for 20 minutes, followed bycooling at 23° C. and humidity of 50% for 24 hours.

After cooling, cross cut peeling tests were carried out based on JISK-5400 with cellophane tapes. Cross cut lines were given with theinterval of 1 mm by a cutter, respectively.

Comparative Application Examples 10 to 19

Evaluations as an Agent for Improving a Printing Property by the FattyAcid Esters Composition Obtained in Comparative Example 1 andCommercially Supplied Fatty Acid Esters Compositions

The same procedures were repeated as described in Application Examples20 to 29 except that there were employed the hexaglycerine monostearateobtained in Comparative Example 1, SY Glystar ML-500 (manufactured bySakamoto Yakuhin Industries), and SY Glystar ML-750 (manufactured bySakamoto Yakuhin Industries).

Evaluations of printing property were based on the following 6 stages.

0: no-removed

1: slightly removed (total length of removed ink of less than 20 mm andwidth of less than 0.1 mm)

2: slightly removed (total length of removed ink of 20 to 50 mm andwidth of 0.1-0.2 mm)

3: fairly removed (total length of removed ink of 50< to 100 mm andwidth of 0.2< to 0.4 mm)

4: further removed (total length of removed ink of 100< to 150 mm andwidth of less than 0.4< to 0.5 mm)

5: considerably removed (total length of removed ink of exceeding 150 mmand width of exceeding 0.5 mm).

Printing properties after 1 hour and 1000 hours from printing wereevaluated. Results are shown in Tables 7 and 8.

TABLE 7 Example 20 21 22 23 24 25 26 27 28 29 (a) P-1 100 (b) D-1 D-4D-5 D-1 D-2 D-3 D-4 D-5 D-5 D-5 0.01 0.01 0.05 3.0 0.1 0.1 0.01 0.010.08 3.0 (c) E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-2 E-3 0.05 4.0 0.1 1.00.2 3.0 0.01 0.5 0.2 0.2 (d) K-1 100 100 500 500 1000 500 500 800 800300 (e) 15.0 15.0 3.0 3.0 1.1 3.0 3.0 1.5 1.5 7.0 (f) 1 1 1 0 0 0 1 1 00 (g) 1 1 1 0 0 0 1 1 0 0

TABLE 8 Comparative Application Example 10 11 12 13 14 15 16 17 18 19(a) P-1 100 (b) D-1 D-4 D-5 D-1 D-2 D-3 D-4 D-5 D-5 D-5 0.01 0.01 0.053.0 0.1 0.1 0.01 0.01 0.08 3.0 (c) E-4 E-4 E-4 E-4 E-4 E-4 E-4 E-4 E-5E-6 0.05 4.0 0.1 1.0 0.2 3.0 0.01 0.5 0.2 0.2 (d) K-1 100 100 500 5001000 500 500 800 800 300 (e) 15.0 15.0 3.0 3.0 1.1 3.0 3.0 1.5 1.5 7.0(f) 1 1 1 0 0 0 1 1 0 0 (g) 5 4 5 5 5 5 5 5 4 4

In the Tables 7 and 8, abbreviations and alphabetically numbering are asfollows.

(a): 100 parts by weight of P-1 (polyacetal polymer) was employed in allthe Application Examples and Comparative Application Examples.

(b): Hindered amine compound (part by weight)

D-1

wherein X is the formula described below,

m is 2, and n is 1.5, and R is the formula described below.

Y is a hydrogen atom.

D-2: In the formula (4), Y is a methyl group, m is 2, and n is 1.5.

D-3: In the formula (4), Y is a methyl group, m is 1, and n is 1.5.

D-4: bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate

D-5: bis(2,2,6,6-tetramethyl-4-piperidyl)adipate

(c):

E-1/hexaglycerine monostearate obtained in Example 17

E-2/octaglycerine monostearate obtained in Example 18

E-3/decaglycerine monostearate obtained in Example 19

E-4/hexaglycerine monostearate obtained in Comparative Example 1

E-5/SY Glystar ML-500 (manufactured by Sakamoto Yakuhin Industries)

E-6/SY Glystar ML-750 (manufactured by Sakamoto Yakuhin Industries)

(d): K-1/Boron nitride having an average particle size of 2 microns as anucleating agent (ppm).

(e): Thickness of skin layer (micron)

(f): Printing property after 1 hour

(g): Printing property after 1000 hours

By the values in (g) of Tables 7 and 8, it is clearly shown that thefatty acid esters composition of the present invention exhibits aneffect for improving printing property in articles molded from thepolyacetal resin composition, compared to the fatty acid esterscomposition obtained in Comparative Example 1 and the commerciallysupplied fatty acid esters compositions.

EXAMPLE 20

Preparation No. 12 of a Fatty Acid Esters Composition of a Polyglycerineas an Agent for Improving Properties of a Thermoplastic Resin

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with100.16 parts by weight of lauric acid and 0.0622 part by weight ofphosphoric acid (a purity of 85%), followed by heating to 140° C.Subsequently, 222.24 parts by weight (molar ratio of glycidol/lauricacid=6) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C.

There was obtained approximately 320 parts by weight of a fatty acidesters composition of a polyglycerine (a hexaglycerine monolauratecomposition).

The composition is designated E-1.

EXAMPLE 21

Preparation No. 13 of a Fatty Acid Esters Composition of a Polyglycerineas an Agent for Improving Properties of a Thermoplastic Resin

Same procedures were repeated as in Example 20 except that 296.32 partsby weight (molar ratio of glycidol/lauric acid=8) of glycidol wasemployed to obtain approximately 390 parts by weight of a fatty acidesters composition of a polyglycerine (an octaglycerine monolauratecomposition).

The composition is designated E-2.

EXAMPLE 22

Preparation No. 14 of a Fatty Acid Esters Composition of a Polyglycerineas an Agent for Improving Properties of a Thermoplastic Resin

Same procedures were repeated as in Example 20 except that 370.40 partsby weight (molar ratio of glycidol/lauric acid=10) of glycidol wasemployed to obtain approximately 465 parts by weight of a fatty acidesters composition of a polyglycerine (a decaglycerine monolauratecomposition).

The composition is designated E-3.

Application Examples 30 to 32

Evaluations as an Agent for Improving a Wetting Property of a PolyacetalResin by the Fatty Acid Esters Composition of the Present Invention

Polyacetal resin (having a trade name of Duracon U10 manufactured byPolyplastics, Ltd.) was mixed with a variety of additives according torespective mixing ratio as shown in Table 8 to prepare a polyacetalresin composition.

Mixing was carried out with a 30-mm twin screw extruder to preparepellets. Results are shown in Table 9.

TABLE 9 Application Example 30 31 32 Additives E-1 E-2 E-3 Amount (% byweight) 0.2 0.2 0.2 Wetting property 38 40 41 (contact angle/degree)Tensile strength 620 615 620 (kgf/cm2) Melt Index 1.0 1.0 1.0 (g/10minutes)

Comparative Application Examples 20 to 28

Evaluations as an Agent for Improving a Printing Property by the FattyAcid Esters Composition Obtained in Comparative Example 1 andCommercially Supplied Fatty Acid Esters Compositions

The same procedures were repeated as in Application Examples 30 to 32except that there were employed the fatty acid esters compositionobtained in Comparative Example 1 and commercially supplied fatty acidesters compositions.

Results are shown in Table 10.

TABLE 10 Comparative Application Example 20 21 22 23 24 25 26 27 28Additives A-1 A-1 A-2 A-3 — B C C D Amount 0.2 0.5 0.5 0.5 — 1.0 1.0 2.02.0 (% by weight) Wetting property 65 41 40 38 72 70 70 58 60 (contactangle/degree) Tensile strength 610 590 600 590 620 570 580 530 510(kgf/cm²) Melt Index 1.0 1.1 1.0 1.0 1.0 1.2 1.0 1.8 1.6 (g/10 minutes)

In the Tables 9 and 10, abbreviations are as follows.

E-1: Fatty acid esters composition of a polyglycerine obtained inExample 20 (a hexaglycerine monolaurate)

E-2: Fatty acid esters composition of a polyglycerine obtained inExample 21 (an octaglycerine monostearate)

E-3: Fatty acid esters composition of a polyglycerine obtained inExample 22 (a decaglycerine monolaurate)

A-1: Commercially supplied fatty acid esters composition of apolyglycerine (a decaglycerine monolaurate)

A-2: Commercially supplied fatty acid esters composition of apolyglycerine (a decaglycerine monostearate)

A-3: Commercially supplied fatty acid esters composition of apolyglycerine (a octaglycerine monolaurate)

B: Glycerine monolaurate

C: Polyethyleneglycol having a molecular weight of 1000

D: Polyethyleneglycol having a molecular weight of 6000

EXAMPLE 23

Preparation No. 15 of a Fatty Acid Esters Composition of a Polyglycerineas an Agent for Improving Properties of a Thermoplastic Resin

A four-necked flask equipped with a tube for supplying nitrogen gas, astirrer, a cooler, a thermostat, and a dropwise funnel was charged with142.25 parts by weight of stearic acid and 0.0622 part by weight ofphosphoric acid (a purity of 85%), followed by heating to 140° C.Subsequently, 222.24 parts by weight (molar ratio of glycidol/stearicacid=6) of glycidol was added drowpwise over 5 hours to allow to reactuntil oxirane oxygen concentration in the reactant attains below 0.1%while maintaining the reaction temperature at 140° C.

There was obtained approximately 260 parts by weight of a fatty acidesters composition of a polyglycerine (a hexaglycerine monostearatecomposition). The composition is designated E1.

EXAMPLE 24

Preparation No. 16 of a Fatty Acid Esters Composition of a Polyglycerineas an Agent for Improving Properties of a Thermoplastic Resin

The same procedures were repeated as described in Example 23 except that370.40 parts by weight (molar ratio of glycidol/stearic acid=10) ofglycidol was employed.

There was obtained approximately 380 parts by weight of a fatty acidesters composition of a polyglycerine (a decaglycerine monostearatecomposition). The composition is designated E2.

Application Examples 33 to 41

Evaluations as an Agent for Improving a Releasing Property of aPolyacetal Resin by the Fatty Acid Esters Composition of the PresentInvention

Polyacetal resin (having a trade name of Duracon-M270 manufactured byPolyplastics, Ltd.) was mixed with a variety of additives according torespective mixing ratio as shown in Table 10 to prepare polyacetal resincompositions.

The polyacetal resin composition was extruded with an extruder toprepare pellets while visually observing the presence or absence offoaming in strands before forming pellets.

Subsequently, the pellets were molded with an injection machine toprepare test pieces. Respective methods for evaluating properties are asfollows.

Tensile strength and shear strength:

The test pieces were placed at the conditions of the temperature of 23°C. and the humidity of 50% for 48 hours, followed by measuring with atensile strength tester (Tensilon manufactured by Orientec, Ltd.) basedon ASTM-D638 and ASTM-D732-85.

Amount of gas in melting:

There were stored 8 g of the pellets in a Melt Index tester at 200° C.for 5 minutes, followed by being discharged while loading. Formaldehydewas caught while discharging under loading, followed by beingquantitatively measured. The amount of formaldehyde is shown by ppmbased on the unit weight of the polyacetal resin.

Continuous injection test:

There was operated an injection machine (manufactured by Toshiba KikaiPlastic Engineering, Ltd.) at the conditions of cylinder temperature of100° C., injection pressure of 750 kg/cm², injection time of 4 seconds,cooling time of 3 seconds, and molding die temperature of 30° C. Aftercontinuously molding articles having a specific shape at the conditions,the amount of resin scraps adhered was visually measured to evaluate areleasing property according to the following 5 stages.

A: resin scraps are not observed at all

B: a minor amount of resin scraps are only observed

C: resin scraps are slightly observed

D: resin scraps are relatively observed

E: resin scraps are considerably observed

Results are shown in Table 11.

TABLE 11 Application Example 33 34 35 36 37 38 39 40 41 Mixing ratio andadditives (A) 100 100 100 100 100 100 100 100 100 (B) fibrous titaniumoxide Average diameter of 0.1 0.2 0.1 0.1 0.1 0.1 0.2 0.1 0.1 fibroustitanium oxide (micron) Average length of fibrous 8 12 8 8 8 8 8 8 8titanium oxide Agent for processing the surface B1 B1 B2 B1 B1 B1 B1 B1B1 of fibrous titanium oxide (part by weight) 25 25 25 45 25 25 25 25 25(C) C1 C1 C1 C1 C2 C1 C1 C1 C1 (part by weight) 0.2 0.2 0.2 0.2 0.2 0.20.2 0.4 0.2 (D) D1 D1 D1 D1 D1 D2 D1 D1 D1 (part by weight) 0.4 0.4 0.40.4 0.4 0.4 0.4 0.4 0.4 (E) E1 E1 E1 E1 E1 E1 E2 E1 E1 (part by weight)0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Properties Tensile strength 830 880820 1050 840 830 825 820 820 (kg/cm²) Shear strength 590 625 580 730 600595 590 580 590 (kg/cm²) Moldability Bubble in molding NB NB NB NB NB NBNB NB B Continuous injection A A A B A A A A A test Amount of gas (ppm)100 70 105 120 95 95 120 60 70

Comparative Application Examples 29 to 34

Evaluations as an Agent for Improving a Releasing Property byCommercially Supplied Fatty Acid Esters Compositions

The same procedures were repeated as described in Application Examples33 to 41 except that there were employed commercially supplied fattyacid esters compositions.

TABLE 12 Comparative Application Example 29 30 31 32 33 34 Mixing ratioand additives (A) 100 100 100 100 100 100 (B) fibrous titanium oxideAverage diameter of 0.3 0.3 0.1 0.1 0.1 0.1 fibrous titanium oxide(micron) Average length of fibrous 15 15 8 8 8 8 titanium oxide Agentfor processing surface B1 B1 B1 B1 B1 — of fibrous titanium oxide (partby weight) 25 45 25 25 25 — (C) C1 C1 — C1 C1 C1 (part by weight) 0.20.2 — 0.2 0.2 0.2 (D) D1 D1 D1 — D1 D1 (part by weight) 0.4 0.4 0.4 —0.4 0.4 (E) E1 E1 E1 E1 — E1 (part by weight) 0.3 0.3 0.3 0.3 — 0.3Properties Tensile strength 900 1100 835 8300 835 — (kg/cm²) Shearstrength 590 630 590 570 580 — (kg/cm²) Moldability Bubble in molding NBNB NB NB NB B Continuous injection D E D D G impossible test Amount ofgas (ppm) 280 510 200 175 180 —

In the Tables 11 and 12, alphabetical abbreviations are as follows.

(A): Polyacetal resin

(B): Titanium oxide whisker

B1: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane

B2: 3-glycidoxypropyltrimethoxysilane

(C): Compound having nitrogen

C1: Melamine

C2: Calcium stearate

(D): Hindered phenol compound

D1: Pentaerythritylterakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]

D2:Triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate]

(E): Fatty acid esters composition of a polyglycerine

E1: Fatty acid esters composition of a polyglycerine (hexaglycerinemonostearate composition) obtained in Example 23

E1: Fatty acid esters composition of a polyglycerine (decaglycerinemonostearate composition) obtained in Example 24

NB: Absence of bubble

B: Presence of bubble

EXAMPLE 25

Preparation No. 1 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for Cosmetics

A four-necked reaction vessel equipped with a tube for supplyingnitrogen gas, a stirrer, a cooler, a thermostat, and a dropwise funnelwas charged with 100.16 parts by weight of lauric acid and 0.0622 partby weight of phosphoric acid (a purity of 85%), followed by heating to140° C. Subsequently, 222.24 parts by weight (molar ratio ofglycidol/lauric acid=6) of glycidol was added drowpwise over 5 hours toallow to react, followed by further allowing to react for 26 hours whilemaintaining the reaction temperature at 140° C.

After cooling, the reactant was taken out to obtain approximately 300parts by weight of a lauric acid esters composition of a polyglycerine.The lauric acid esters composition of a polyglycerine prepared wasanalyzed by the analytical condition No. 1 in the HPLC analysis asdefined hereinabove. It was identified from the chart that thecomposition (a hexaglycerine monolaurate composition) contains amonolaurate of polyglycerine of 87.7%.

EXAMPLE 26

Preparation No. 2 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for Cosmetics

The same procedures were repeated as described in Example 25, exceptthat there was employed 296.32 parts by weight (molar ratio ofglycidol/lauric acid=8) of glycidol. It was identified from the chartthat the composition (an octaglycerine monolaurate composition) containsa monolaurate of polyglycerine of 84.5% by the analytical condition No.1 in the HPLC analysis as defined hereinabove.

EXAMPLE 27

Preparation No. 3 of a Fatty Acid Esters Composition of a Polyglycerineas an Additive for Cosmetics

The same procedures were repeated as described in Example 25, exceptthat there was employed 370.4 parts by weight (molar ratio ofglycidol/lauric acid=10) of glycidol. It was identified from the chartthat the composition (a decaglycerine monolaurate composition) containsa monolaurate of polyglycerine of 77.2% by the analytical condition No.1 in the HPLC analysis as defined hereinabove.

Application Examples 42 to 44 and Comparative Application Examples 35 to37

Evaluations as a Water-in-oil Type-emulsified Composition for Cosmetics

There was prepared a water-in-oil type-emulsified composition forcosmetics based on the components and the mixing ratio as describedbelow, respectively.

Liquid paraffin (23% by weight)

Vaseline (6.5% by weight)

Micro-crystalline wax (0.2% by weight)

Lanolin (4.0% by weight)

Bleached bees wax (1.2% by weight)

Tri(caprylic-capric)glyceryl (12% by weight)

Butyl paraoxybenzoate (0.1% by weight)

Glycerine (15% by weight)

Ethyl paraoxybenzoate (0.1% by weight)

Perfume (0.2% by weight)

Purified water (34.2% by weight), (19.2% by weight only in ComparativeApplication Example 36)

1,3-butyleneglycol (15% by weight only in Comparative ApplicationExample 36)

Fatty acid esters composition of a polyglycerine (3.5% by weight)

Application Examples:

42: Fatty acid esters composition of a polyglycerine (a hexaglycerinemonolaurate composition) prepared in Example 25

43: Fatty acid esters composition of a polyglycerine (an octaglycerinemonolaurate composition) prepared in Example 26

44: Fatty acid esters composition of a polyglycerine (a decaglycerinemonolaurate composition) prepared in Example 27

Comparative Application Examples

35: Hexaglycerine monolaurate composition prepared in ComparativeExample 4 <by the reaction of a fatty acid with a polyglycerine>

36: SY Glystar ML-500 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

37: SY Glystar MO-750 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

Total weight (100% by weight)

In Application Examples 42 to 44, an oily phase containing a fatty acidesters composition of a polyglycerine and glycerine was dissolved byheating to 75° C. Independently, a water phase containing purified waterwas heated to 75° C.

The water phase was added into the oily phase to emulsify while mixingwith an emulsifier, followed by cooling and adding perfumes at 45° C.,and then cooling to 30° C.

In Comparative Application Examples, the same procedures were repeatedas employed in Application Examples except that 1,3-butyleneglycol wasmixed only in Comparative Application Example 36.

Results are shown in Table 13.

TABLE 13 Comparative Application Examples Application Example Property42 43 44 35 36 37 Viscosity immediately after prepared 1570 1830 19702540 2430 2660 Viscosity after 3 months 1570 1830 1970 2540 2430 2660Stability for a long time of period (3 months) Room temperature − − − +− − −5° C. − − − − − − 40° C. − − − + ± ± Feel in use + + + + ± ±

In the Table 13, methods and standard for evaluation were according tothe following stages.

(a) Viscosity: It was measured with a Brookfield viscometer at 25° C.

(b) Stability after 3 months: It was visually evaluated after placed atvarious temperatures for several months according to the followingstages.

−: presence of a separation in emulsified composition

±: presence of a slight separation in emulsified composition

+: presence of a remarkable separation in emulsified composition

(c) Feel in use: Tackiness, spreadability, and oily touch were evaluatedby organoleptic tests of 10 professional panelists.

−: a good feel in use

±: a slightly unsatisfied feel in use

+: a slightly unsatisfied feel in use

Application Examples 45 to 48

Evaluations as a Water-in-oil Type-emulsified Composition for Cosmetics

In Application Example 45, a water-in-oil type-emulsified compositionwas evaluated as an emulsion for cleansing in which the followingcomponents are mixed.

Liquid paraffin (23% by weight)

Vaseline (6.5% by weight)

Micro-crystalline wax (0.2% by weight)

Lanolin (4.0% by weight)

Tri(caprylic-capric)glyceryl (12% by weight)

Bleached bees wax (1.2% by weight)

Glycerine (15% by weight)

Fatty acid esters composition of a polyglycerine prepared in Example 25(3.5% by weight)

Butyl paraoxybenzoate (0.1% by weight)

Ethyl paraoxybenzoate (0.1% by weight)

Perfume (0.2% by weight)

Purified water (34.2% by weight)

Total (100% by weight)

In Application Example 46, a water-in-oil type-emulsified compositionwas evaluated as an emulsion for body in which the following componentsare mixed.

Squalane (15% by weight)

Liquid paraffin (8.0% by weight)

Vaseline (6.5% by weight)

Micro-crystalline wax (0.2% by weight)

Lanolin (4.0% by weight)

Lanolin cholestearyl of a fatty acid (0.5% by weight)

Olive oil (12.0% by weight)

Bleached bees wax (1.2% by weight)

Glycerine (15% by weight)

Fatty acid esters composition of a polyglycerine prepared in Example 25(3.5% by weight)

Decaglyceryl tristearate (0.5% by weight)

Butyl paraoxybenzoate (0.1% by weight)

Methyl paraoxybenzoate (0.1% by weight)

Perfume (0.2% by weight)

Purified water (34.2% by weight)

Total (100% by weight)

In Application Example 47, a water-in-oil type-emulsified compositionwas evaluated as an emulsion for preventing rough hands in which thefollowing components are mixed.

Application Examples 49 to 51 and Comparative Application Examples 38 to41

Evaluations as a Transparent Liquid Composition for Cosmetics

There was prepared a transparent liquid composition for cosmetics basedon the components and the mixing ratio as described below, respectively.

POE oleylether (15.0% by weight)

1,3-butyleneglycol (19.0% by weight)

Squalane (11.0% by weight)

Tri(caprylic-capric)glycerine (11.0% by weight)

Purified water (29.0% by weight)

Fatty acid esters composition of a polyglycerine or an other additive(15.0% by weight)

Application Examples:

49: Fatty acid esters composition of a polyglycerine (a hexaglycerinemonolaurate composition) prepared in Example 25

50: Fatty acid esters composition of a polyglycerine (an octaglycerinemonolaurate composition) prepared in Example 26

51: Fatty acid esters composition of a polyglycerine (a decaglycerinemonolaurate composition) prepared in Example 27

Comparative Application Examples

38: Hexaglycerine monolaurate composition prepared in ComparativeExample 4 (by the reaction of a fatty acid with a polyglycerine)

39: SY Glystar ML-500 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

40: SY Glystar MO-750 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

41: Sucrose laurate

Total weight (100% by weight)

Results are shown in Table 14.

TABLE 14 Application Comparative Examples Application Example 49 50 5138 39 40 41 Property HLB 10.0 10.5 11.0 100.0 10.5 10.0 10.5 AppearanceT T T ST T T ST L L L L C L L Spreadability G G G G P G G Appearanceafter T T T ST ST ST ST 1 month L L L L C L L In the Table 14,abbreviations are follows. HLB: Hydrophile lipophile balance T:Transparent ST: Semi transparent L: Liquid-state C: Cream-state G: GoodP: Poor

Application Examples 52 to 58

Evaluations as a Transparent Liquid Composition for Cosmetics

In Application Example 52, a transparent liquid composition forcosmetics was evaluated as a lotion for body in which the followingcomponents are mixed. The components (a) to (c), components (g) and (h)were homogeneously mixed, followed by dispersing the components (d) to(f).

Subsequently, the component (i) was gradually added to obtain atransparent lotion for body having HLB value of 10.5.

The transparent lotion for body was diluted with a proper amount of warmwater, resulting in exhibiting a wet and smooth feel in use on body.

(a) Fatty acid esters composition of a polyglycerine obtained in Example27 (7.4% by weight)

(b) POE (3) oleylether having HLB value of 6.5 (8.1% by weight)

(c) 1,3-butanediol (19.0% by weight)

(d) Tri(caprylic-capric)glycerine (5.5% by weight)

(e) Squalane (11.0% by weight)

(f) Hohoba oil (1.8% by weight)

(g) Perfumes (0.5% by weight)

(h) Antiseptic (0.4% by weight)

(i) Purified water (46.3% by weight)

In Application Example 53, a transparent liquid composition forcosmetics was evaluated as a lotion for bathing in which the followingcomponents are mixed. The components (a) to (c), components (g) and (h)were homogeneously mixed, followed by dispersing the components (d) to(f). Subsequently, the component (i) was gradually added to obtain atransparent lotion for bathing having HLB value of 10.5. The transparentlotion for bathing was quickly dispersed, resulting in forming anemulsified

(a) Fatty acid esters composition of a polyglycerine obtained in Example27 (7.6% by weight)

(b) Diglycerine monooleate having HLB value of 6.5 (12.0% by weight)

(c) 1,3-butanediol (13.0% by weight)

(d) Tri(caprylic-capric)glycerine (11.5% by weight)

(e) Squalane (11.0% by weight)

(f) Avocado oil (0.4% by weight)

(g) Perfumes (0.5% by weight)

(h) Antiseptic (0.3% by weight)

(i) Purified water (43.7% by weight)

In Application Example 54, a transparent liquid composition forcosmetics was evaluated as a lotion for cleansing in which the followingcomponents are mixed. The components (a) to (c), components (g) and (h)were homogeneously mixed, followed by dispersing the components (d) to(f). Subsequently, the component (i) was gradually added to obtain atransparent lotion for cleansing having HLB value of 10.0 which has agood spreadability and a smooth feel in use on skin. Furthermore,washing with water after cleansing was very readily, and it exhibited arefreshing feel in use.

(a) Fatty acid esters composition of a polyglycerine obtained in Example27 (11.2% by weight)

(b) Sorbitan monoisostearate having HLB value of 5.0 (12.6% by weight)

(c) 1,3-butanediol (17.5% by weight)

(d) Tri(2-ethylhexanic acid)glyceryl (16.0% by weight)

(e) Squalane (14.0% by weight)

(f) Nuts oil (0.5% by weight)

(g) Perfumes (0.3% by weight)

(h) Antiseptic (0.4% by weight)

(i) Purified water (27.5% by weight)

In Application Example 55, a transparent liquid composition forcosmetics was evaluated as a lotion for massaging in which the followingcomponents are mixed. The components (a) to (c), components (g) and (h)were homogeneously mixed, followed by dispersing the components (d) to(f). Subsequently, the component (i) was gradually added to obtain atransparent lotion for massaging having HLB value of 10.7 which has agood spreadability and a smooth feel in use on skin. Furthermore, it wasreadily washed with water after massaging, and was capable of providinga fresh-looking skin.

(a) Fatty acid esters composition of a polyglycerine obtained in Example27 (12.0% by weight)

(b) POE(3)oleylether having HLB value of 6.5 (9.6% by weight)

(c) 1,3-butanediol (19.0% by weight)

(d) Liquid paraffin (15.0% by weight)

(e) Squalane (10.0% by weight)

(f) Hohoba oil (2.0% by weight)

(g) Perfumes (0.3% by weight)

(h) Antiseptic (0.3% by weight)

(i) Purified water (31.8% by weight)

In Application Example 56, a transparent liquid composition forcosmetics was evaluated as a lotion for an emollient pack in which thefollowing components are mixed. The components (a) to (c), components(h) and (i) were homogeneously dissolved, followed by dispersing thecomponents (d) to (f). Subsequently, the component (k) was graduallyadded, followed by adding the components (g) and (j) to obtain a lotionfor an emollient pack having HLB value of 10.5 which has a goodspreadability, an easy coatability in using on face, and makes skin wetand smooth after use. Furthermore, washing with water was very easy evenafter packing.

(a) Fatty acid esters composition of a polyglycerine obtained in Example27 (8.9% by weight)

(b) Diglycerine monooleate having HLB value of 6.5 (14.0% by weight)

(c) 1,3-butanediol (22.0% by weight)

(d) Tri(2-ethylhexanic acid)glyceryl (13.0% by weight)

(e) Squalane (12.0% by weight)

(f) Hohoba oil (2.5% by weight)

(g) Extracts from aloe (1.0% by weight)

(h) Perfumes (0.3% by weight)

(i) Antiseptic (0.3% by weight)

(j) Polyvinylpyrrolidone (0.3% by weight)

(k) Purified water (25.7% by weight)

In Application Example 57, a transparent liquid composition forcosmetics was evaluated as a hair treatment in which the followingcomponents are mixed. The components (a) to (d), components (i) and (j)were homogeneously dissolved, followed by dispersing the components (e)to (h). Subsequently, the component (l) was gradually added, followed byadding the component (k) to obtain a hair treatment having HLB value of8.8 which is a transparent liquid. The hair treatment can be directlyemployed for wetted hairs, and also it was capable of rinsing with tepidwater even after lapse of an appropriate time. flairs exhibited a neatfeel in touch.

(a) Fatty acid esters composition of a polyglycerine obtained in Example27 (4.6% by weight)

(b) Diglycerine monooleate having HLB value of 6.5 (16.2% by weight)

(c) Dimethylammonium distearyl chloride (1.8% by weight)

(d) 1,3-butanediol (18.0% by weight)

(e) Dodecanol octylate (7.0% by weight)

(f) Squalane (16.0% by weight)

(g) Hohoba oil (2.3% by weight)

(h) Silicon oil (0.3% by weight)

(i) Perfumes (0.3% by weight)

(j) Antiseptic (0.3% by weight)

(k) Dyes (a proper amount)

(l) Purified water (33.3% by weight)

In Application Example 58, a transparent liquid composition forcosmetics was evaluated as a base material for medicines in which thefollowing components are mixed. The components (a) to (c), and thecomponent (g) were homogeneously dissolved, followed by dispersing thecomponents (d) to (f). Subsequently, the component (h) was graduallyadded to obtain a base material for medicines. It was transparent,liquid, and excellent in spreadability.

(a) Fatty acid esters composition of a polyglycerine obtained in Example27 (8.3% by weight)

(b) Diglycerine monooleate having HLB value of 6.5 (11.4% by weight)

(c) 1,3-butanediol (13.0% by weight)

(d) Tri(caprylic-capric)glycerine (7.0% by weight)

(e) Squalane (15.0% by weight)

(f) Olive oil (1.0% by weight)

(g) Antiseptic (0.2% by weight)

(h) Purified water (44.1% by weight)

Application Examples 59 to 64 and Comparative Application Examples 42 to44

Evaluations as a Gel-like Emulsified Composition for Cosmetics

In the Application Examples arid Comparative Application Examples,methods and standard for evaluation were according to the followingstages.

(a) Stability after placing at 40° C. for 60 days: It was visuallyevaluated according to the following stages.

+: absence of a separation in composition

−: presence of a separation upper or lower layer in composition

(b) Viscosity: It was measured with a Brookfield viscometer (spindle #4)at 25° C.

(c) Feel in use: It was evaluated by organoleptic tests of 5professional panelists.

+: Good evaluation by all the members

−: Good evaluation by members not exceeding 4

There was prepared a gel-like emulsified composition for cosmetics basedon the components and the mixing ratio as described below, respectively.

(a) 1,3-butanediol (3.0% by weight)

(b) Purified water (3.0% by weight)

(c) Liquid paraffin (75.0% by weight)

(d) Glycerine (15.0% by weight)

(e) Perfumes (0.50% by weight)

(g) Fatty acid esters composition of a polyglycerine (3.5% by weight)

Application Example 59

Composition Obtained in Example 25

Application Example 60

Composition Obtained in Example 26

Application Example 61

Composition Obtained in Example 27

Comparative Application Example 42

Hexaglycerine Monolaurate Composition Prepared in Comparative Example 4<by the Reaction of a Fatty Acid with a Polyglycerine>

Comparative Application Example 43

SY Glystar ML-500 Manufactured by Sakamoto Yakuhin Kogyo, Ltd.

Comparative Application Example 44

SY Glystar MO-750 Manufactured by Sakamoto Yakuhin Kogyo, Ltd.

TABLE 15 Comparative Application Examples Application Example Property59 60 61 42 43 44 Stability (for 1 month at 40 C) + + + + + + Viscosity(cps) 7000 7600 8100 9000 9500 9700 Feel in use + + + − − +

In Application Example 62, there was prepared a gel-like emulsifiedcomposition for cosmetics based on the components and the mixing ratioas described below, respectively.

The composition was evaluated as gel for a cleansing.

(a) 1,3-butanediol (2.0% by weight)

(b) Purified water (1.6% by weight)

(c) Liquid paraffin (56.0% by weight)

(d) Glycerine (37.0% by weight)

(e) Sodium hyaluronate (0.002% by weight)

(f) Perfumes (0.20% by weight)

(g) Fatty acid esters composition of a polyglycerine obtained in Example27 (3.0% by weight)

In Application Example 63, there was prepared a gel-like emulsifiedcomposition for cosmetics based on the components and the mixing ratioas described below, respectively.

The composition was evaluated as a gel for massaging.

(a) 1,3-butanediol (2.0% by weight)

(b) Purified water (2.8% by weight)

(c) Liquid paraffin (25.0% by weight)

(d) Trioctanic glyceryl (25.0% by weight)

(e) Glycerine (42.0% by weight)

(f) Sodium hyaluronate (0.002% by weight)

(g) Perfumes (0.20% by weight)

(h) Fatty acid esters composition of a polyglycerine obtained in Example27 (3.0% by weight)

In Application Example 64, there was prepared a gel-like emulsifiedcomposition for cosmetics based on the components and the mixing ratioas described below, respectively.

The composition was evaluated as a wiping liquid for making-up.

(a) Decaglycerylmonomilystate (1.5% by weight)

(b) 1,3-butanediol (2.0% by weight)

(c) Purified water (11.3% by weight)

(d) Liquid paraffin (40.0% by weight)

(e) Glycerine (42.0% by weight)

(f) Sodium hyaluronate (0.001% by weight)

(g) Perfumes (0.20% by weight)

(h) Fatty acid esters composition of a polyglycerine obtained in Example25 (3.0% by weight)

All the gel-like emulsified compositions for cosmetics in ApplicationExamples 62 to 64 exhibited an excellent stability and excellent feel inuse.

Application Examples 65 to 67 and Comparative Application Examples 45 to48

Evaluations as a Composition for Tooth Paste

In Application Example 65, there was prepared a composition for toothpaste based on the components and the mixing ratio as described below,respectively.

(a) Dihydrate of calcium secondary phosphate (45.00% by weight)

(b) Carboxymethyl cellulose (0.50% by weight)

(c) Carrageenan (0.50% by weight)

(d) Glycerine (10.0% by weight)

(e) Sorbitol (10.0% by weight)

(f) Water (28.70% by weight)

(g) Fatty acid esters composition of a polyglycerine obtained in Example25 (2.00% by weight)

(h) Perfumes (1.00% by weight)

(i) Sodium saccharide (0.20% by weight)

(j) Sterilizer and Antiseptic (0.10% by weight)

In Application Example 66, the same components in Application Example 65were employed except that there was employed the fatty acid esterscomposition of a polyglycerine obtained in Example 26 as the component(g).

In Application Example 67, the same components in Application Example 65were employed except that there was employed the fatty acid esterscomposition of a polyglycerine obtained in Example 27 as the component(g).

In Comparative Application Example 45, the same components inApplication Example 65 were employed except that there was employed thehexaglycerine monolaurate composition prepared in Comparative Example 4<by the reaction of a fatty acid with a polyglycerine> as the component(g).

In Comparative Application Example 46, the same components inApplication Example 65 were employed except that there was employed SYGlystar ML-500 manufactured by Sakamoto Yakuhin Kogyo, Ltd. as thecomponent (g).

In Comparative Application Example 47, the same components inApplication Example 65 were employed except that there was employed SYGlystar ML-750 manufactured by Sakamoto Yakuhin Kogyo, Ltd. as thecomponent (g).

In Comparative Application Example 48, the same components inApplication Example 65 were employed except that there was employed asucrose laurate as the component (g).

Results are shown in Table 16.

TABLE 16 Comparative Application Examples Application Example 65 66 6745 46 47 48 Foaming ability 480 500 460 290 300 260 250 Foamed volumefeeling in mouth G G G SP P SP SP

In the Application Examples and Comparative Application Examples,methods and standard for evaluation were according to the followingstages.

(a) Foaming ability: It was evaluated by measuring volume of foam afteragitating at 60V with a National mixer (MX-420) for 90 seconds.Beforehand, samples were prepared by suspending 5 g of composition fortooth paste in 50 ml of water warmed at 30° C.

(b) Foamed volume feeling in mouth: It was evaluated by organoleptictests of 5 panelists.

G : Presence of foaming

SP: Presence of slightly foaming

P : Absence of foaming

As shown in Table 16, there can be obtained a composition for toothpaste having excellent foaming ability, a refreshing feel in use,no-irritation at mucous membrane in mouth, no-depression of enzymes byemploying the fatty acid esters composition of a polyglycerine specifiedin the present invention.

Application Examples 68 to 71 and Comparative Application Examples 49 to53

Evaluations as a Cleaning Agent Compositions

In Application Example 68, there was prepared a cleaning agentcomposition based on the components and the mixing ratio as describedbelow, respectively.

(a) Glycerine succinate monolaurate (5.0 parts by weight)

(b) Fatty acid esters composition of a polyglycerine obtained in Example25 (11.0 parts by weight)

(c) Sodium tripolyphosphate (35.0 parts by weight)

(d) Sodium sulfuric anhydride (49.0 parts by weight)

(e) Deionized water (100 parts by weight)

The components (c) and (d) were mixed with a mixture composed of (a) and(b), and further component (e) was added, followed by mixing at 60° C.to obtain a homogeneous liquid.

Subsequently, sulfuric acid was added in order to adjust to PH of 7.0,followed by spray-drying to obtain a cleaning agent composition.

In a 500-ml beaker, 1.3 g of the cleaning agent composition wasdissolved in 400 ml of tap water at 25° C. while agitating with amagnetic stirrer to obtain a solution.

Separately, 4 glass plates having 5 cm L×2 cm W×0.5 mm t were coatedwith 0.03-0.04 g of beef tallow, respectively, followed by immersinginto the solution for 5 minutes.

Cleaning ability was evaluated by the ratio (%) of area on which beeftallow was washed with respect to total area.

Results are shown in Table 17.

TABLE 17 Component (b) Component (a) CP (%) Application Examples 68 No.1 B1 A1 34    2 B2 A1 39    3 B3 A1 43    4 B3 A2 53 ComparativeApplication Example 49 No. 1 B4 A1 25    2 B5 A1 23    3 B6 A1 21    4B6 A2 24    5 B7 — 2

In the Table 17, abbreviations are as follows.

B1: Fatty acid esters composition of a polyglycerine obtained in Example25

B2: Fatty acids esters composition of a polyglycerine obtained Example26

B3: Fatty acid esters composition of a polyglycerine obtained Example 27

B4: Hexaglycerine monolaurate composition prepared in ComparativeExample 4 <by the reaction of a fatty acid with a polyglycerine>

B5: SY Glystar ML-500 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

B6: SY Glystar ML-750 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

B7: Sucrose laurate

A1: Glycerine succinate monolaurate

A2: Glycerine succinate monodecanate

In Application Example 69, there was prepared a cleaning agentcomposition based on the components and the mixing ratio as describedbelow, respectively.

(a) Glycerine succinate monolaurate (12.0 parts by weight)

(b) Fatty acid esters composition of a polyglycerine obtained in Example25 (5.0 parts by weight)

(c) Sodium tripolyphosphate (35.0 parts by weight)

(d) citric acid (2.5 parts by weight)

(e) Sodium sulphate (45.5 parts by weight)

The cleaning agent composition was dissolved into water to obtain anaqueous solution having 0.33% by weight.

The solution was employed to wash soy beans, resulting in showing highwashing power and sterilizing ability.

In Application Example 70, there was prepared a cleaning agentcomposition based on the components and the mixing ratio as describedbelow, respectively.

(a) Glycerine succinate monomilystate (15.0 parts by weight)

(b) Fatty acid esters composition of a polyglycerine obtained in Example25 (2.0 parts by weight)

(b) Fatty acid esters composition of a polyglycerine obtained in Example27 (5.0 parts by weight)

(c) Sodium pyrophosphate (30.0 parts by weight)

(d) Phosphoric acid (2.0 parts by weight)

(e) Sodium sulphate (46.0 parts by weight)

The cleaning agent composition was dissolved into water to obtain anaqueous solution having 0.20% by weight.

The solution was employed to wash tomatoes, resulting in showing highwashing ability.

In Application Example 71, there was prepared a cleaning agentcomposition based on the components and the mixing ratio as describedbelow, respectively.

There was adjusted PH of an aqueous solution containing 0.10% by weightof glycerine succinate monolaurate and 0.030% by weight of the fattyacid esters composition of a polyglycerine obtained in Example 25 to 4,5, and 7 with an aqueous solution of sodium hydroxide to obtain threeaqueous solutions having different PHs. Sterilizing ability wasevaluated as follows concerning the three aqueous solutions havingdifferent PHs.

Triangular flasks containing 10 g of soy beans and 90 ml of therespective aqueous solution were vibrated for 5 minutes.

After vibrated for 5 minutes, respective washed soy beans were mixedwith 90 ml of sterilized water in a 100-ml flask, followed by placing ina thermostatically-controlled oven at 35° C. for 20 hours.

After placing for 20 hours, soy beans were minutely crushed togetherwith sterilized water in a homogenizer, followed by filtering with asterilized gauze to separate solid.

A filtered liquid which is a starting liquid was diluted into ten times,hundred times, and thousand times, respectively, with a sterilizedphysiological aqueous solution of sodium chloride. 1 ml of the startingliquid and 3 diluted liquid were poured into 4 laboratory dishes,respectively.

Subsequently, there was poured 15-20 ml of a standard agar culturemedium which was kept at 50° C. after sterilized in a high pressure,followed by immediately mixing, respectively.

The 4 laboratory dishes were settled until the agar culture mediacompletely coagulate. After coagulated, the 4 laboratory dishes werecultivated at 35° C. for 2 days to count the number of colonies by aconventional method. As a result, the number of microorganisms was lessthan 10 per 1 g of soy beans in all the laboratory dishes. Forreferences, the same procedures were repeated except that water havingPh of 7 was employed in place of the solution containing the fatty acidesters composition of a polyglycerine to obtain the number ofmicroorganisms of 5.5×10⁶ per 1 g of soy beans.

Application Examples 72 to 77 and Comparative Application Examples 54 to56

Evaluations as a Foaming Composition for Cleaning

TABLE 18 Comparative Application Examples Application Example 72 73 7454 55 56 A1 1.0 A2 1.0 A3 1.0 A4 1.0 A5 1.0 A6 1.0 Property Stability GG G P G G Stability (Deterioration ratio of protein): It was E E E I E EFoaming ability G G G I I I Durability of Foam (Stability of Foam) G G GI I I Feel in use G G G I G G

In the Table 18, A1 to A6 correspond to the following composition,respectively.

A1: Fatty acid esters composition of a polyglycerine obtained in Example25

A2: Fatty acid esters composition of a polyglycerine obtained in Example26

A3: Fatty acid esters composition of a polyglycerine obtained in Example27

A4: Hexaglycerine monolaurate composition prepared in ComparativeExample 4 <by the reaction of a fatty acid with a polyglycerine>

A5: SY Glystar ML-500 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

A6: SY Glystar ML-750 manufactured by Sakamoto Yakuhin Kogyo, Ltd.

In Application Examples 72-74 and Comparative Application Examples54-56, there was prepared a cleaning agent composition based on thecomponents and the mixing ratio as described below, respectively.

Fatty acid esters composition of a polyglycerine (1.0% by weight)

Cetyl alcohol (2.0% by weight)

Ethyl alcohol (50.0% by weight)

Purified water (42.0% by weight)

Liquified Petroleum Gas/L.P.G. (5.0% by weight)

In Application Example 75, there was prepared a cleaning agentcomposition based on the components and the mixing ratio as describedbelow, respectively.

Fatty acid esters composition of a polyglycerine obtained in Example 25(2.5% by weight)

Cetstearyl alcohol (2.5% by weight)

Perfumes (0.2% by weight)

Purified water (53.5% by weight)

Ethyl alcohol (35.0% by weight)

Liquified Petroleum Gas/L.P.G. (7.0% by weight)

In Application Example 76, there was prepared a cleaning agentcomposition based on the components and the mixing ratio as describedbelow, respectively.

Fatty acid esters composition of a polyglycerine obtained in Example 25(1.5% by weight)

Cetyl alcohol (3.0% by weight)

Saffron oil (0.1% by weight)

Perfumes (0.2% by weight)

Purified water (36.2% by weight)

Ethyl alcohol (55.0% by weight)

Liquified Petroleum Gas/L.P.G. (4.0% by weight)

In Application Example 77, there was prepared a cleaning agentcomposition based on the components and the mixing ratio as describedbelow, respectively.

Fatty acid esters composition of a polyglycerine obtained in Example 25(1.2% by weight)

Behenyl alcohol (0.5% by weight)

POE(4)stearylether (1.0% by weight)

Orange oil (0.1% by weight)

Perfumes (0.2% by weight)

Purified water (47.1% by weight)

Ethyl alcohol (45.0% by weight)

Liquified Petroleum Gas/L.P.G. (5.0% by weight)

The cleaning agent composition in Application Examples 75-77 exhibitedan excellent stability, foaming ability, durability of foam, andcleaning ability.

In the Application Examples and Comparative Application Examples,methods and standard for evaluation were according to the followingstages.

(a) Stability (Deterioration ratio of protein): It was evaluated bydeterioration ratio (HDR %) of hemoglobin.

It exhibited a good relationship with an irritating intensity for eyesaccording to a Draze method. HDR%=[(LAOC−LAOD)/(LAOC)]×100

LAOC: Light absorption degree by a control sample

LAOD: Light absorption degree after deteriorating by a test sample

E: HDR of <5%

G: HDR of 5% to <15%

I: HDR of 15% to <50%

B: HDR of not less than 50%

(b) Cleaning ability: It was measured by a cleaning process in which afixed amount of artificial fatty skin dirt containing an ultraviolet rayabsorbent was coated on a rubber plate, and then rubbing was carried outat three cycles with a paper towel containing a sample liquid under afixed loading.

 The artificial fatty skin dirt after cleaning was recovered with asolvent, and then the amount of the ultraviolet ray absorbent wasmeasured to evaluate as follows.

G: Cleaning ability of not less than 60%

I: Cleaning ability of 40% to <60%

B: Cleaning ability of not more than 40%

(c) Foaming ability: It was evaluated by a process that there were mixedan agent for foaming (spraying) a mixture and the mixture in a fixedratio to prepare an aerosol, and the aerosol was filled in a can forspraying, and then the aerosol was sprayed onto hands at −5° C., 25° C.,and 30° C., respectively.

 Foaming ability was evaluated by organoleptic tests.

G: Good

I: Insufficient

(d) Durability of Foam (Stability of Foam): It was evaluated by aprocess that the aerosol was sprayed, there was measured a ratio (Fr %)between the volume of foam immediately after spraying and the volumeafter 30 minutes.

Fr %=[(Volume of foam after 30 minutes)/(Volume of foam immediatelyafter spraying)]×100

G: Fr of not less than 80%

I: Fr of 50% to <80%

B: Fr of <50%

(e) Feel in use: It was evaluated by a method that 5 g of respectivesample was employed for washing hairs, and then wiped with towels. At 30minutes after wiping, a refreshing feel in hairs was evaluated byorganoleptic tests of 8 panelists according to the following 5 stages.

Excellent: 5

Good: 4

Normal: 3

Slightly poor: 2

Poor: 1

 Evaluations were shown by average points of the 8 panelists.

(a) Stability: It was evaluated by a method that samples were preservedat temperatures of −5° C., 0° C., 25° C., and 30° C. for 1 month, andthe samples were sprayed, conditions of foam at the temperatures and atthe 25° C. were visually observed to evaluate by the following stages.

G: Appropriate as a foaming composition for cleaning

P: Inappropriate as a foaming composition for cleaning

EXAMPLE 28

Preparation of a Highly-purified Fatty Acid Esters Composition of aPolyglycerine from the Composition (a Decaglycerine MonolaurateComposition) Obtained in Example 5

The composition obtained in Example 5 and 2% by weight of water wascharged into a flask. Subsequently, the flask was heated to 135° C.while stirring under refluxing, followed by maintaining at thetemperature for 2 hours. Subsequently, the flask was heated to 140° C.Distillation in reduced pressures was carried out while maintaining atthe temperature in order to remove water for 4 hours to obtain ahighly-purified fatty acid esters composition of a polyglycerine.Reduced pressure degree was finally 10 mmHg.

There was carried out HPLC analysis with the analytical condition No. 2relating to the highly-purified fatty acid esters composition of apolyglycerine. FIG. 24 (ML-10) is a chart obtained by the HPLC analysis.It was identified from the chart that the composition contains amonolaurate of polyglycerine of 81.26% by weight, polyglycerine of 8.20%by weight, and other components of 10.54% by weight by the analyticalcondition No. 2 in the HPLC analysis as defined hereinabove.

Comparative Examples 16 and 17

HPLC Analysis by the Analytical Condition No. 2 Relating to a Fatty AcidEsters Composition of a Polyglycerine which is Commercially Supplied

As fatty acid esters composition which is commercially supplied preparedby the reaction of a polyglycerine with a fatty acid, SY Glystar ML-750manufactured by Sakamoto Yakuhin, Ltd. and Sunsoft Q-12S manufactured byTaiyo Kagaku, Ltd. were analyzed by the analytical condition No. 2 inHPLC analysis. FIG. 25 (ML-750) and FIG. 26 (Q-12S) are a respectivechart obtained by the HPLC analysis.

It was identified from the charts that the respective compositionscontain a monolaurate of polyglycerine of 44.92% by weight,polyglycerine of 14.16% by weight, and other components of 40.82% byweight, and a monolaurate of polyglycerine of 48.80% by weight,polyglycerine of 26.88% by weight, and other components of 24.32% byweight by the analytical condition No. 2 in the HPLC analysis as definedhereinabove.

Comparative Example 18

HPLC Analysis by the Analytical Condition No. 3 Relating to a Fatty AcidEsters Composition of a Polyglycerine which is Commercially Supplied

As fatty acid esters composition which is commercially supplied preparedby the reaction of a polyglycerine with a fatty acid, SY Glystar ML-500manufactured by Sakamoto Yakuhin, Ltd. was analyzed by the analyticalcondition No. 3 in HPLC analysis.

FIG. 27 is a chart obtained by the HPLC analysis. It was identified fromthe charts that the respective compositions contain a monolaurate ofpolyglycerine of 38.20% by weight, polyglycerine of 6.17% by weight, andother components of 55.64% by weight.

While the invention has been described in detail and with reference tothe specific embodiments thereof, it will be apparent to those skilledin the art that various changes and modifications can be made thereinwithout departing from the spirit and scope thereof.

We claim:
 1. A resin composition which comprises: A. a thermoplasticresin, and, B-1. a fatty acid esters composition of a polyglycerinecontaining more than 70% of a fatty acid monoester represented by thegeneral formula (1) described below: RCO—[OCH₂CH(OH)CH₂]_(n)—OH  (1)wherein R is an alkyl group, an alkenyl group, or a hydroxylgroup-substituted alkyl group which has a carbon number ranging from 6to 21, and n is an integer of at least 4, based on a peak area ratiodetected using an ultraviolet ray absorption detector in a highperformance liquid chromatographic analysis method; or B-2. ahighly-purified fatty acid esters composition of a polyglycerine havingan oxirane oxygen concentration of below 100 ppm, said oxiraneconcentration is defined by the titration method defined in Cd. 9-57 ofJournal of American Oil Chemists' Society, or having a ratio of below0.01%, said ratio is a peak area value of a chemical shift between 2.7ppm and 2.8 ppm assigned by methylene proton derived from an oxiranegroup with respect to a peak area value of a chemical shift between 3.4ppm and 4.4 ppm assigned by methylene proton and methine proton derivedfrom a polyglycerine with a proton NMR.
 2. A resin composition whichcomprises: A. a thermoplastic resin, and, B. a fatty acid esterscomposition of a polyglycerine containing more than 70% of a fatty acidmonoester represented by the general formula (1) described below: RCO—[OCH₂CH(OH)CH₂]_(n)—OH  (1) wherein R is an alkyl group, an alkenylgroup, or a hydroxyl group-substituted alkyl group which has a carbonnumber ranging from 6 to 21, and n is an integer of at least 4, based ona peak area ratio detected using an ultraviolet ray absorption detectorin a high performance liquid chromatographic analysis method.
 3. A resincomposition which comprises: A. a thermoplastic resin, and, B. ahighly-purified fatty acid esters composition of a polyglycerine havingan oxirane oxygen concentration of below 100 ppm, said oxiraneconcentration is defined by the titration method defined in Cd. 9-57 ofJournal of American Oil Chemists' Society, or having a ratio of below0.01%, said ratio is a peak area value of a chemical shift between 2.7ppm and 2.8 ppm assigned by methylene proton derived from an oxiranegroup with respect to a peak area value of a chemical shift between 3.4ppm and 4.4 ppm assigned by methylene proton and methine proton derivedfrom a polyglycerine with a proton NMR.
 4. A resin composition as setforth in claim 1, wherein said thermoplastic resin is a polyvinylchloride resin.
 5. A resin composition as set forth in claim 1, whereinsaid thermoplastic resin is a styrene-based resin.
 6. A resincomposition as set forth in claim 5, wherein said styrene-based resin isat least one selected from the group consisting of a styrenehomopolymer, a styrene-methylmethacrylate copolymer, astyrene-methylmethacrylate-acrylonitrile copolymer, astyrene-methylmethacrylate-methylacrylate copolymer, and astyrene-methylmethacrylate-methylacrylate-cyclohexylmaleimide copolymer.7. A resin composition as set forth in claim 5, wherein saidstyrene-based resin is further mixed with a phosphorous compound and,optionally, a polyalkyleneglycol.
 8. A resin composition as set forth inclaim 1, wherein said thermoplastic resin is a methylmethacrylate-basedresin.
 9. A resin composition as set forth in claim 8, wherein saidmethylmethacrylate-based resin is further mixed with pentaerythritols orfatty acid esters thereof.
 10. A resin composition as set forth in claim1, wherein said thermoplastic resin is a polyacetal resin.
 11. A resincomposition as set forth in claim 10, wherein said polyacetal resin hasa Melt Index of less than
 2. 12. A resin composition as set forth inclaim 10, wherein an article molded from said acetal resin has a contactangle of less than
 50. 13. A resin composition as set forth in claim 10;wherein said fatty acid esters composition is mixed together with ahindered amine compound.
 14. A resin composition as set forth in claim10, wherein said fatty acid esters composition is mixed together with ahindered phenol-based compound, fibrous titanium oxide, and at least oneselected from the group consisting of a compound having nitrogen, ahydroxide of alkaline metal or alkaline earth metal, and a metal salt ofa carboxylic acid or an inorganic acid.
 15. A resin composition as setforth in claim 10, wherein said resin composition is molded as a shutterfor a disk or a magnetic tape cartridge.
 16. A resin composition as setforth in claim 10, wherein said resin composition is molded as an inkjet nozzle.